Foam inhibitor



United States Patent 3,259,586 FOAM INHIBITOR Woodrow J. Dickson, La Habra, and Fred W. Jenkins,

Buena Park, Calif., assignors to Petrolite Corporation No Drawing. Original application Aug. 4, 1960, Ser.

No. 47,386, new Patent No. 3,200,106, dated Aug. 10,

1965. Divided and this application Aug. 6, 1963, Ser.

8 Claims. (Cl. 252321) This application is a division of Ser. No. 47,386 filed August 4, 1960, now US. Patent No. 3,200,106.

This invention relates to bnanched polyalkylene polyamines and to derivatives thereof. More particularly, this invention relates to said branched po lyamines and to branched polyamine derivatives containing various groups, such as the oxyalkylated, acy-lated, alkylated, carbonylated, olefinated, etc., derivatives thereof, pre pared by introducing such groups individually, alternately, in combination, etc., including for example, derivatives prepared by varying the order of adding such groups, by increasing the number and order of adding such groups, and the like.

This invention also relates to methods of using these products, which have an unexpectedly broad spectrum of uses, for example, as demulsifiers for water-in-oil emulsions; as demulsifiers for oil-in-Water emulsions; as corrosion inhibitors; as fuel oil additives for gasoline, diesel fuel, jet fuel, and the like; as lubricating oil additives; as scale preventatives; as chelating agents or to form chelates which are themselves useful, for example, as antioxidants, gasoline stabilizers, fungicides, etc.; as flotation agents, for example, as flotation collection agents; as asphalt additives or anti-stripping agents for asphaltmineral aggregate compositions; as additives for compositions useful in acidizing calcareous strata of oil wells; as additives for treating water used in the secondary recovery of oil and in disposal wells; as additives used in treating oil-well strata in primary oil recovery to enhance the flow of oil; as emulsifiers for both oil-in- Water and water-in-oil emulsions; as additives for slushing oils; as additives for cutting oils; as additives for oil to prevent emulsification during transport; as additives for drilling muds; as agents useful in removing rnud sheaths from newly drilled wells; as dehazing or foginhibiting agents for fuels; as additives for preparing sand or mineral slurries useful in treating oil wells to enhance the recovery of oil; as agents for producing polymeric emulsions useful in preparing water-vapor impermeable paper board; as agents in paraffin solvents; as agents in preparing thickened silica aerogel lubricants; as gasoline additives to remove copper therefrom; as deicing and antistalling agents for gasoline; as antiseptic, preservative, bactericidal, bacteriostatic, germicidal, fungicidal agents; as agents for the textile industry, for example, as mercerizing assistants, as wetting agents, as rewettlng agents, as dispersing agents, as detergents, as penetrating agents, as softening agents, as dyeing assistants, as anti-static agents, and the like; as additives for rubber latices; as entraining agents for concrete and cements; as anti-static agents for rugs, floors, upholstery, plastic and wax polishes, textiles, etc.; as detergents useful in metal cleaners, in floor oils, in dry cleaning, in general cleaning, and the like; as agents useful in leather processes such as in flat liquoring, pickling, acid degreasing, dye fixing, and the like; as agents in metal pickling; as additives in paints for improved adhesion of primers, in preventing water-spotting in lacquer; as antiskinners for pigment flushing, grinding and dispersing, as antifeathering agents in ink; as agents in the preparation of Wood pulp and pulp slurries, as emulsifiers for insecti cidal compositions and agricultural sprays such as DDT, 24D (T oxaphene), chlordane, nicotine sulfate, hexachloracyclohexane, and the like; as agents useful in building materials, for example, in the water repellent treatment of plaster, concrete, cement, roofing materials, floor sealers; as additives in bonding agents for various insulatingbuilding materials; and the like.

X RE -ENE:

I NH: y

wherein R is an alkylene group such as ethylene, propylene, butylene and other homologues (both straight chained and branched), etc., but preferably ethylene; and x, y and z are integers, x being for example, from 4 to 24 or more but preferably 6 to 18, y being for example 1 to 6 or more but preferably 1 to 3, and 2 being for example 0-6 but preferably 0-1. The x and y units may be sequential, alternative, orderly or randomly distributed.

The preferred class of polyamines includes those of the formula where n is an integer, for example, 1-20 or more but preferably l-3, wherein R is preferably ethylene, but may be propylene, butylene, etc. (straight chained or branched).

The preferred embodiments are presented by the following formula:

I NH,

The radicals in the brackets may be joined in a headto-head or a head-to-tail fashion. Compounds described by this formula wherein n=l3 are manufactured and sold as Polyamines N-400, N-800, N-1200 etc. Polyamine N-400 has the above formula wherein 11:1.

These compounds may be prepared by a wide variety of methods. One method comprises the reaction of ethanolamine and ammonia under pressure over a fixed bed of a metal hydrogenation catalyst. By controlling the conditions of this reaction one may obtain varying amounts of piperazine and polyamines as well as the branched chain polyalkylene polyamine useful in this invention. This process is described in Australian application No. 42,189, now Australian Patent No. 233,766, and in the German Patent No. 14,480 (March 17, 1958) reported in Chem. Abstracts, August 10, 1949, 14,129.

These branched polyamines can also be prepared by the following reactions:

tween the acylating agent and the branched polyamine reactant. In order to facilitate the removal of this water, to effect a more complete reaction in accordance with the principle of Le Chatelier, a hydrocarbon solvent which forms an azeotropic mixture with water can be added to the reaction mixture. Heating is continued with the liquid reaction mixture at the preferred reaction temperature, until the removal of water by azeotropic distillation has substantially ceased. In general, any hydro- H R C OH H H H CHr-CHr NHPCH2CH2NCH2CH2NH2 IIICH2CHzN-CHaCH2 I O=C G=O it B H H S0201 H II Triethylene tetramino N-CHzCHrN-CI-IzCHa-N NCHaCHzNCH2CH:-N I l I followed by hydrolysis 0:? CH2 (i=0 0:? (iJHa CI=O R (i /Hg R R (3H2 R OH Cl i NH:

Variations on the above procedure can produce other branched polyamines.

The branched nature of the polyamine imparts unusual properties to the polyamine and its derivatives.

For the sake of brevity and to simplify presentation, the invention will be described by the selection of one branched polyamine to illustrate the reactions and uses thereof (i.e. N-400). However, it is to be understood that such presentation is purely for illustration and the invention should not be limited thereto.

ACYLATION A wide variety of acylating agents can be employed. Acylation is carried out under dehydrating condition, i.e., water is removed. Any of the well-known methods of acylation can be employed. For example, heat alone, heat and reduced pressure, heat in combination with an azeotroping agent, etc., are all satisfactory.

The temperature at which the reaction between the acylating agent and the branched polyalkylenepolyamine is effected is not too critical a factor. Since the reactions involved appear to be an amide-formation reaction and a condensation reaction, the general temperature conditions for such reactions, which are well known to those skilled in the art, are applicable.

Acylation is conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and the reaction products. In general, the reaction is carried out at a temperature of from 120 to 280 C., but preferably at 140 to 200 C.

The product formed on acylation will vary with the particular conditions employed. First the salt, then the amide is formed. If, however, after forming the amide at a temperature between 140-250 C., but usually not above 200 C., one heats such products at a higher range, approximately 250-280 C., or higher, possibly up to 300 C. for a suitable period of time, for example,

CH: r NH:

carbon solvent which forms an azeotropic mixture with water can be used. It is preferred, however, to use an aromatic hydrocarbon solvent of the benzene series. Nonlimiting examples of the preferred solvent are benzene, toluene, and xylene. The amount of solvent used is a variable and non-critical factor. It is dependent on the size of the reaction vessel and the reaction temperature selected. Accordingly, a sufiicient amount of solvent must be used to support the azeotropic distillation, but a large excess must be avoided since the reaction temperature will be lowered thereby. Water produced by the reaction can also be removed by operating under reduced pressure. When operating with a reaction vessel equipped with a reflux condenser provided with a water takeofi trap, sufficient reduced pressure can be achieved by applying a slight vacuum to the upper end of the condenser. The pressure inside the system is usually reduced to between about 50 and about 300 millimeters. If desired, the water can be removed also by distillation, while operating under relatively high temperature conditions.

The time of reaction between the acylating agent and the branched polyamine reactant is dependent on the weight of the charge, the reaction temperature selected, and the means employed for removing the water from the reaction mixture. In practice, the reaction is continued until the formation of water has substantially ceased. In general, the time of reaction will vary between about 4 hours and about ten hours.

Although a wide variety of carboxylic acids produce excellent products, carboxylic acids having more than 6 carbon atoms and less than 40 carbon atoms but preferably 8-30 carbon atoms give most advantageous products. The most common examples include the detergent forming acids, i.e., those acids which combine with alkalies to produce soap or soap-like bodies. The detergentforming acids, in turn, include naturally-occurring fatty acids, resin acids, such as abietic acid, naturally occurring petroleum acids, such as naphthenic acids, and carboxy acids, produced by the oxidation of petroleum. As will be subsequently indicated, there are other acids which have somewhat similar characteristics and are derived from somewhat different sources and are difierent in structure, but can be included in the broad generic term previously indicated.

Suitable acids include straight chain and branched chain, saturated and unsaturated, aliphatic, alicyclic, fatty, aromatic, hydroaromatic, and aralkyl acids, etc.

Examples of saturated aliphatic monocarboxylic acids are acetic, proprionic, butyric, valeric, caproic, eptanoic, caprylic, nonacoic, capric, undecauoic, lauric, tridecanoic, myriatic, pentadecanoic, palmitic, heptadecanoic, stearic, nonadecanoic, eicosanoic, heneicosanoic, docosanoic, tricosanoic, tetracosanoic, pentacosanoic, cerotic, heptacosanoic, montanic, nonacosanoic, melissic and the like.

Examples of ethylenic unsaturated aliphatic acids are acrylic, methacrylic, cr-otonic, anglic, teglic, the pentenoic acids, the hexenoic acids, for example, hydrosorbic acid, the heptenoic acids, the octenoic acids, the nonenoic acids, the decenoic acids, for example, obtusilic acid, the undecenoic acids, the dodecenoic acids, for example, lauroleic, linderic, etc., the tridecenoic acids, the tetradecenoic acids, for example, myristoleic acid, the pentadecenoic acids, the hexadecenoic acids, for example, palmitoleic acid, the heptadeoenoic acids, the octodecenoic acids, for example, petrosilenic acid, oleic acid, elardic acid, the nonadecenoic acids, for example, the eicosenoic acids, the docosenoic acids, for example, erucic acid, brassidic acid, cetoleic acid, the tetradosenic acids, and the like.

Examples of dienoic acids are the pentadienoic acids, the hexadienoic acids, for example, sorbic acid, the octadienoic acids, for example, linoleic, and the like.

Examples of the trienoic acids are the octadecatrienoic acids, (for example, linolenic acid, eleostearic acid, pseudoeleostearic acid, and the like.

Carboxylic acids containing functional groups such as hydroxy groups can be employed. Hydroxy acids, particularly the alpha hydroxy acids include glycolic acid, lactic acid, the hydroxyvaleric acids, the hydroxy caproic acids, the hyd-roxyheptanoi-c acids, the hydroxy caprylic acids, the hydroxynonanoic acids, the hydroxycapric acids, the hydroxydecanoic acids, the hydroxy lauric acids, the hydroxy tridecanoic acids, the hydroxymyristic acids, the hydroxypentadecanoic acids, the hydroxyp-almitic acids, the hydroxyhexadecanoic acids, the hydroxyheptadecanoic acids, the hydroxy stearic acids, the hydroxyoctadecenoic acids, for example, rioinoleic acid, ricinelardic acid, hydroxyoctadecynoic acids, for example, ricinstearoli-c acid, the hydroxyelcosanoic acids, for example, hydroxyarachidic acid, the hydroxydocosanoic acids, for example, hydroxybehenic acid, and the like.

Examples of .acetylated hydroxyacids are ricinoleyl lactic acid, acetyl ricinoleic acid, chloroacetyl ricinoleic acid, and the like.

Examples of the cyclic aliphatic carboxylic acids are those found in petroleum called naphthenic acids, hydrocarbic and chau-moogric acids, cyclopentane carboxyl-ic acids, cyclohexauecarboxylic acid, campholic acid, fenchlolic acids, and the like.

Examples of aromatic monocarboxylic acids are benzoic acid, substituted benzoic acids, for example, the toluic acids, the xyleneic acids, alkoxy ibe-nzoic acid, phenyl benzoic acid, naphthalene carboxylic acid, and the like.

Mixed higher fatty acids derived from animal or vegetable sources, for example, lard, cocoanut oil, rapeseed oil, sesame oil, palm kernel oil, palm oil, olive oil, corn oil, cottonseed oil, sardine oil, tallow, soyabean oil, peanut oil, castor oil, seal oils, whale oil, shark oil, and other fish oils, teaseed oil, partially or completely hydrogenated animal and vegetable oils are advantageously employed.

Fatty and similar acids include those derived from various waxes, such as beeswax, spermaceti, montan wax, Japan wax, coccerin and carnauba wax. Such acids include carnaubic acid, cerotic acid, lacceric acid, montanic acid, psyllastearic acid, etc. One may also employ higher molecular weight carboxylic acids derived by oxidation and other methods, such .as from paraffin wax, petroleum and similar hydrocarbons; resinic and hydroaromatic acid-s, such as hexahydrobenzoic acid, hydrogenated naphthoic, hydrogenated carboxy diphenyl, naphthenic, and abietic acid; Twitchell fatty acids, carboxydiphenyl pyridine carboxylic acid, blown oils, blown oil fatty acids and the like.

Other suitable acids include phenylstearic acid, benzoylnonylic acid, cetyloxybutyric acid, cetyloxyacetic acid, chlorstearic acid, etc.

Examples of the polycarboxylic acids are those of the aliphatic series, for example, oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, nonanedicarboxylic acid, decanedicarboxylic acids, undecanedicarboxylic acids, and the like.

Examples of unsaturated aliphatic polycarboxylic acids are fumaric, maleic, mesocenic, citraconic, glutonic, itaconic, muconic, aconitic acids, and the like.

Examples of aromatic polycarboxylic acids are phthalic, isophthalic acids, terephthalic acids, substituted derivatives thereof (e.g. alkyl, chloro, alkoxy, etc., derivatives), biphenyldicarboxylic acid, diphenylether dicarboxylic acids, diphenylsulfone dicarboxylic acids and the like.

Higher aromatic polycarboxylic acids containing more than two carboxylic groups are himimellitic, trimellitic, trimesic, mellophanic, prehnitic, pyromellitic acids, mellitic acid, and the like.

Other polyc'ar-boxyl'ic acids are the dimeric, trirneric, and polymeric acids, for example, dilinoleic, trilinoleic, and other polyacids sold by Emery Industries, and the like. Other polycarboxylic acids include those containing ether groups, for example, diglycolic acid. Mixtures of the above acids can be advantageously employed.

In addition, acid precursors such as acid anhydrides, esters, acid halides, glycerides, etc., can be employed in place of the free acid.

Examples of acid anhydrides are the alkenyl succinic acid anhydrides.

Any alkenyl succinic acid anhydride or the corresponding acid is utilizable [for the production of the reaction products of the present invention. The general structural formulae of these compounds are:

Anhydride R-C HC Acid wherein R is an alkenyl radical. The alkenyl radical can be straight-chain or branched-chain; and it can be saturated at the point of unsaturation by the addition of a substance which adds to olefinic double bonds, such as hydrogen, sulfur, bromine, chlorine, or iodine. It is obvious, of course, that there must be at least two carbon atoms in the alkenyl radical, but there is no real upper limit to the number of carbon atoms therein. However, it is preferred to use an alkenyl succinic acid anhydride reactant having between about 8 and about 18 carbon atoms per alkenyl radical. Although their use is less desirable, the alkenyl succinic acids also react, in accordance with this invention, to produce satisfactory reaction products. It has been found, however, that their use necessitates the removal of water formed during the reaction and also often causes undesirable side reactions to occur to some extent. Nevertheless, the alkenyl succinic acid anhydrides and the alkenyl succinic acids are interchangeable for the purposes of the present invention. Accordingly, when the term alkenyl succinic acid anhydride, is used herein, it must be clearly understood that it embraces the alkenyl succinic acids as well as their anhydrides, and the derivatives thereof in which the ole.

finic double bond has been saturated as set forth hereinbefore. Non-limiting examples of the alkenyl succinic acid anhydride reactant are ethenyl succinic acid anhydrides; ethenyl succinic acid; ethyl succinic acid anhydride; propenyl succinic acid anhydride; sulfurized propenyl succinic acid anhydride; butenyl succinic acid; 2-methylbutenyl succinic acid anhydride; 1,2-dichloropentyl succinic acid anhydride; hexenyl succinic acid anhydride; hexyl succinic acid; sulfurized 3-methylpentenyl succinic acid anhydride; 2,3-dimethylbutenyl succinic acid anhydride; 3,3-dimethylbutenyl succinic acid; 1,2-dibromo-Z-ethylbutyl succinic acid; heptenyl succinic acid anhydride; 1,2-diiodooctyl succinic acid; octenyl succinic acid anhydride; 2-methyl-heptenyl succinic acid anhydride; 4-ethylhexenyl succinic acid; 2-isopropylpentenyl succinic acid anhydride; nonenyl succinic acid anhydride;

2-propylhexenyl succinic acid anhydride; decenyl succinic acid; decenyl succinic acid anhydride; 5-methyl-2-isopropylhexenyl succinic acid anhydride; 1,2-dibromo-2-ethyloctenyl succinic acid anhydride; decyl succinic acid anhydride; undecenyl succinic acid anhydride; 1,2-dichloroundecyl succinic acid anhydride; 1,2-dichloro-undecyl succinic acid; 3-ethyl-2-t-butylpentenyl succinic acid anhydride; dodecenyl succinic acid anhydride; dodecenyl succinic acid; 2-propylnonenyl succinic acid anhydride; 3-butyloctenyl succinic acid anhydride; tridecenyl succinic acid anhydride; tetradecenyl succinic acid anhydride; hexadecenyl succinic acid anhydride; sulfurized octadecenyl succinic acid; octadecyl succinic acid anhydride; 1,Z-dibromo-2-methylpentadecenyl succinic acid anhydride; 8-propylpentadecyl succinic acid anhydride; eicosenyl succinic acid anhydride; 1,Z-dichloro-2-methylnonadecenyl succinic acid anhydride; 2-octyldodecenyl uccinic acid; 1,2-diiodotetracosenyl succinic acid anhydride; hexacosenyl succinic acid; hexacosenyl succinic acid anhydride; and hentriacontenyl succinic acid anhydride.

The methods of preparing the alkenyl succinic acid anhydrides are well known to those familiar with the art. The most feasible method is by the reaction of an olefin with maleic acid anhydride. Since relatively pure olefins are difficult to obtain, and when thus obtainable, are often too expensive for commercial use, alkenyl succinic acid anhydrides are usually prepared as mixtures by reacting mixtures of olefins with maleic acid anhydride. Such mixtures, as well as relatively pure anhydrides, are utilizable herein.

In summary, without any intent of limiting the scope of the invention, acylation includes amidification, the formation of the cyclic amidine ring, the formation of acid imides such as might occur when anhydrides such as the alkenylsuccinic acids are reacted, i.e.,

wherein P=branched polyamine residue, polymers as might occur when a dicarboxylic acid is reacted intermolecularly with the branched polyamine, cyclization as might occur when a dicarboxylic acid reacts intramolecularly with the polyamine as contrasted to intermolecular reactions, etc. The reaction products may contain other substances. Accordingly, these reaction products are most accurately defined by a definition comprising a recitation of the process by which they are produced, i.e., by acylation.

The moles of acylating agent reacted with the branched polyamine will depend on the number of acylation reactive positions contained therein as well as the number of moles of acylating agent one wishes to incorporate into the molecule. We have advantageously reacted l to 10 moles of acylating agent per mole of Polyamine N-400, but preferably 1 to 6 moles. With Polyamine N-O and N-1200, twice and three times as many moles of acylat ing agent can be employed respectively, i.e. with Polyamine N800, 1-20 moles, preferably 1-12; with N1200, 1-30, but preferably 1-18. Optimum acylation will depend on the particular application.

The following examples are illustrative of the preparation of the acylated branched polyamines.

The following general procedure is employed in acylating. The branched polyamine is mixed with the desired ratio of acid and a suitable azeotroping agent is added. Heat is then applied. After the removal of the calculated amount of water (1 to 2 equivalents per carboxylic acid group of the acid employed), heating is stopped and the azeotroping agent -is evaporated under vacuum. The temperature during the reaction can vary from 80 to 200 C. Where the formation of the cyclic amidine type structure is desired the maximum temperature is generally 180-250 C. and more than one mole of water per carboxy lic group is removed. The reaction times range from 4 to 24 hours. Here again, the true test of the degree of reaction is the amount of water removed.

Example 3A In a 5 liter, 3 necked flask furnished with a stirring device, thermometer, phase separating trap, condenser and heating mantle, 1 mole (400 grams) of Polyamine N-400 is dissolved in an equal weight of xylene, i.e., 400 grams. 845 grams of oleic acid (3 moles) is added to the polyamine with stirring in about ten minutes. The react-ion mixture is then heated gradually to about C. in half an hour and then held at about C. over a period of 3 hours until 54 grams (3 moles) of water is collected in the side of the tube. The solvent is then removed with gentle heating under reduced pressure of approximately 20 mm. The product is a dark, viscous, xylene-soluble liquid.

Example 3-A The prior example is repeated except that the final reaction temperature is maintained at 240 C. and 90 grams (5 moles) of water are removed instead of 54 grams (3 moles). Infrared analysis of the product indicates the presence of a cyclic amidine ring.

The following examples of acylated branched polyamines are prepared in the manner of the above examples from Polyamine N-400 by employing 400 grams of polyamine in each example. The products obtained are dark, viscous materials.

In the examples the symbol A identified the acylated branched polyamine. Thus, specifically 1-A, represents acylated Polyamine N-400, which polyamine is employed in all the reactions of the following table.

TABLE I.ACYLATED PRODUCTS OF POLYAMINE N400 XYALKYLATION d M These branched polyamines can be oxyalkylated in Ex A w f Water Remwed the conventional manner, for example, by means of an N G Pogirttgne M1 G alpha-beta alkylene oxide such as ethylene oxide, proame mm 055 I pylene oxide, butylene oxide, octylene oxide, a higher M 1 182 alkylene oxide, styrene oxide, glycide, methylglycide, etc., 182 or combinatlons thereof. Dependlng on the particular 13% application desired, one may combine a large proportion 95 of alkylene oxide, particularly ethylene oxide, propylene 3g 10 oxide, a combination or alternate additions or propylene h 108 ox1de and ethylene oxide, or smaller proportions thereof 3:1 5.1 9 in relation to the branched polyarnine. Thus, the molar 6:1 5.9 106 3:1 M 54 who of alkylene oxide to branched polyamme can range 2 2.8 3% within Wide limits, for example, from a 1:1 mole ratio 58 to a ratio of 1000:1, or higher, but preferably 1 to 200. 52 For example, in demulsification extremely high alkylene 3 40 oxide ratios are often advantageously employed such as 22 200-300 or more moles of alkylenev oxide per mole of 5 1 branchedpolyamine. Onthe other hand, for certain ap- 0 2% plications such as corrosion prevention and use as fuel 0.6651 411 74 oil additives, lower ratios of alkylene oxides are advan- 21 g? tageously employed, i.e., 1/ 10-25 moles of alkylene oxide per mole of branched polyamine. By proper control, dedo 532, 3;; i 4 sired hydrophilic or hydrophobic properties are imparted 10-21111: A1lrenyl (6...) Sue 966 3:1 5.2 04 to, the composition. As is well known, oxyalkylation re- 10 Az gggg (322) 644 2:1 21 38 actions are conducted under a Wide variety of conditions, do. 644 2:1 0.2 3.6 at low or high pressures, at loW or high temperatures, in P 35% :3 3% the presence or absence of catalyst, solvent, etc. For 460 0. 5:1 1.1 20 instance oxyalkylation reactions can be carried out at :38 1:3 g? temperatures of from 80200 C., and pressures of from 3 6 3:1 3.1 56 10 to 200 p.s.i., and times of from 15 min. to several f5: i3 i5 days. Preferably oxyalkylation reactions are carried out 107.2 0.8:1 0.8 14 at 80 to 120 C. and 10 to 30 p.s.i. For conditions of g; 'fgi 8:2 2 oxyalkylation reactions see US. Patent 2,792,369 and 8 4 0 8 1 0 0 other patents mentioned therein. 7 j "f5 Oxyalkylation is too Well known to require a full S 330; 990 3 54 discussion. For purpose of brevity reference is made 5 V to Parts 1 and 2 of US. Patent No. 2,792,371, dated 1 211 4 72 May 14, 1957, to Dickson in which particular attention 830 6 108 is directed to the various patents Wh1ch describe typical oxyalkylation procedure. Furthermore, manufacturers of *Chief substituent oi oiticica oil is the glyceride oflicanic acid: alkylene Qxldes furnlsh eXtenSlVe informatlofl 35 t0 t e use of oxides. For example, see the technical bulletin entitled, Ethylene Oxide, which has been distributed CH (CH -(CH=CH), OH g( CH C H by the Jefferson Chemical Company, Houston, Texas. Note also the extensive bibliography in this bulletin and Th fgllowing table pre nt specific illust atio f the large number of patents which deal with oxyalkylation compounds other than N-400 and its derivatives. processes.

TABLE IA.ACYLATED PRODUCTS Acid Mols of Acid Water Exam- Branched Per Mols of Removed pie Polyamine Branched Name Grams Polyarmne Moles Grams 18-A N-SOO 01610 (282 564 2:1 2.2 39.6 18-41;..- N-800- do.. 282 1:1 1.0 34.2 19%.--- N-'800 Dimeric (600). 1,800 3:1 2.9 52.3 19-11 N-800. do 1,200 2:1 2.1 37.8 20-A1 N-SOO Alkenyl Suceinic An- 532 2:1

hydride (266). 20-112". d0 266 L; L 21-.4 Diglycolic (134) v 134 1:1 1. 0 18 22-A Maleic Anhydride(98) 98 1:1 23A Naphthenic (33) Sunap- 330 1:1 2.1 37.8

tic AeidB 24-11.. Acetic 60 1 1 1. 1 19.6 25A Diphenolic (286) 286 1:1 1.1 19.6 26-111.. Stearic (284) 568 2: 1 1. 8 32. 4 26-11 do 284 1:1 1.9 34.2 27A Dimerie (600) 600 1:1 1. 1 19.6 28A Benzoic (122) 122 1 1 0. 9 16. 2 29A 'Ierephthalic (166) 166 1:1 0.8 1 14.4 30-A Diphenolic (286) 286 1: 1 1. 0 18. 0 31-11---- Laurie (200) 200 1:1 1. 2 21. 6 32-211--. Oleic (282) 846 3:1 3.1 55.8 32-11 do 564 2:1 1.9 34.2 62-11 -do 282 1:1 1.0 18.0 33-11-- Acetic (60) 240 4: 1 4. 0 72. 0

. 11 The symbol employed to designate oxyalkylation is O. Specifically 1O represents oxyalkylated Polyamine N-400.

In the following oxyalkyl ations the reaction vessel em 12 tion is highly exothermic. The reaction mass now contains 1 mol of N4OO and a total of 22 mols of reacted ethylene oxide.

Example 1O ployed is a stainless steel autoclave equipped with the 5 A portion of the reaction mass of Example is 21 t i for 3 1 l 52 :32 2 2 3 ;352: 5: transferred to another autoclave and an additional amoulrlit an 011 6 means an e 1 e W 1c f EtO dd d. The reaction mass now containst e this type of apparatus. The stirrer is operated at a speed i i z N 400 to 40 mols of Eta of 250 r.p.m. The branched polyamine, Polyamine N- Exam [8 400, dissolved in an equal weight of xylene is charged into 10 I p a the reactor. The autoclave is sealed, swept with nitro- The addition of ethyle'ne OXlde Example 141:15 1 gen, stirring started immediately and heat applied, The tlnucd until a molar ratio of 1 mol of N-400 to 75 mo 5 temperature is allowed to rise to approximately 100 C. of Eto 1S reachedat which time the addition of the alkylene oxide is started Example e and added continuously at such speed as it is absorbed The addition f ethylene id to E l 1 i by the reaction mixture. When the rate of oxyalkylatron continued until a molar ratio f 1 f N 4()0 to 83 slows down appreciably, which generally occurs after mols f 0 i h d about 15 moles of ethylene oxide are added or after about E l 1 O 10 moles of propylene oxide are added, the reaction vessel xamp e 'I is Opened and an oxyalkylation y t s a d (in 2 The addition of ethylene oxide to the Example 1-0 is weight percent of the total reactants present). The catcontinued until a molar ratio of 1 mol of N-400 to 105 alyst employed in the examples is sodium methylate. ol f H0 i r h d, Thereupon the autoclave is flushed out as before and oxyalkylation completed. In the case of oxybutylation, Example 2 O1 oxyoctylation, oxystyrenation, and other oxyalkylations, grams of N-400 are Charge/d 1M0 a c'onvefltlontal etc., the catalyst is added at the beginning of the operation. Stainless Steel autoclave- The temperature 15 falsed t0 Example 1 0 120 C., the autoclave is flushed with nitrogen and sealed. 1 Then 290 grams of propylene oxide (5-mols) are added Using the oxyalkylation apparatus and procedure stated slowly at 120 C. A sample is taken at this point and above, the following compounds are prepared: 400 grams labeled 2O This sample contains 5 mols of PrO for (1 mol) of Polyamine 400 are charged into a stainless each mol of N400. It is a dark very viscous liquid at steel autoclave, swept with nitrogen, stirring started, and room temperature. autoclave sealed. The temperature is allowed to rise to Example approximately 100 C. and ethylene oxide is injected continuously until 220 grams (5 mols) total had been E i f fg of proliylene. OXlde 3 3 commune; added over a one-half hour period. This reaction is exoauto: g g: an 1 9 thermic and requires cooling to avoid a rise in temperaso 2 if y f a d e 1 d 3 ave 18 a i ture. The reaction mass is transferred to a suitable cong g W1 f i an i e l OX1 IS tainer. Upon cooling to room temperature, the reaction 3 i y 1 1 1 J 3 mass isadark extremelyviscous liquid. 40 mace Samp e 15 a en 18 Pomt an a e e 2-O This compound now contains 10 mols of propylene Example 2 oxide for each mol of N-400. The same procedure as Example 1-O is used exactly Example 2-O except that 396 grams of ethylene oxide (9 mols) is added Th 1 f 2 O d d to 400 grams (1 mol) of Polyamin-e N400 This retional 6 3 i i r iis oii p io pylengdriidg zir e izac ie d z kzaiii- Zita/0n material is a dark VISCOLIS liquid at room tempera- P16 is taken at this point and labeled 3 3 com Example tains 21 mols of propylene oxide for each mol of N-400. Th 1 1 E I 1 O u d d 396 At lrlclaom temlplfrlature the product is a dark thick liquid.

e same 'oceoure as xam e 1s se an grams of ethy lene oxide (9 mols are adiled to 400 grams 2-O 2 3: 2 6: 2 F02 continued to produce examples (1 mol) of Polyamine N-400. After this reaction is A summary of oxyalkylated products produced from completed, the autoclave is opened and 20 grams of sodi- N-400 is presented in the following Table II. um methylate are added. The autoclave is then fiushed The Roman numerals, (I), (II), and (III) besides the again with nitrogen and an additional 572 grams (13 moles of oxide added indicate the order of oxide addition mols) of ethylene oxide 18 added at C. This reac- (I) first, (II) second and (III) third, etc.

TABLE IL-OXYALKYLATED PRODUCTS [Moles of oxide/mole N-400] Ex. EtO Wgt. PO Wt. B o Wt.

Moles (g) Mgles (gs) M811 es (gg) Phy sical properties 1Oi 5 220 Dark viscous liquid.

Do. Semi-solid. Solid.

Do. Do. Do. Dark viscous liquid.

Do. Do. Do. Do. Do. Do. Do. D0. D0.

TABLE II.Continued Ex. EtO Wgt. PrO Wgt. BuO Wgt. Physical properties Moles (g.) Moles (g.) Moles (g.)

220 40 (II) 2, 320 Dark viscous liquid. 484 63 (II) 3, 654 Do. 748 88 (II) 3,872 Do.

2, 332 19 (II) 1,102 Semi-solid.

4, 312 95 (II) 4, 510 Dark thick liquid.

352 19 (I) 1,102 Do.

968 39 (I) 2,262 Do. 792 96 (I) 5, 568 D0.

4, 080 105 (I) 6,090 Do.

2, 420 (I) 290 Solld.

220 18 (H) 1, 044 Dark viscous liquid. 220 (III) 290 (I) Do.

396 23 (III) 1, 334 D0. 836 19 (II) 1, 102 Do.

1,980 75 (I) 4, 350 (II) Do.

Octylene oxide 5 moles, 635 g. D0.

Octylene oxide 8 moles, 1,016 g. Do.

Styrene oxide 4 moles, 480 g. Do.

Styrene oxide 7 moles, 840 g. Do.

Epoxide 201 1 mole, 280 g. Solid.

The following table presents specific illustration of compounds other than N-400 and its derivatives.

TABLE IIA.OXYALKYLATED P ROD UCTS Example Mols of Oxide Per M01 Branched of Branched Polyamine Physical Polyamine Properties EtO PrO BuO 4 (In D S tyrene Oxide, 5 mols Solld.

Octylene Oxide, 10 mols Do.

Dark viscous ACYLATION THEN OXYALKLATION Prior acylated branched polyamines can be oxyalkylated in the above manner by starting with the acylated branched polyamine instead of the unreacted amine. Non-limiting examples are presented in the following tables. The symbol employed to designate an acylated, oxyalkylated branched polyamine is A0. Specifically 1-A O represents acylated, then oxyalkylated polyamine N-400.

Example 3A O For this example an autoclave equipped to handle alkylene oxides is necessary. 1156 grams (1 mole) of 3A (N 400+3 moles Oleic Acid minus three moles H O) are charged into the autoclave. Following a nitrogen purge and the addition of 120 grams of sodium methylate, the temperature is raised to 135 C. and 5683 grams of E0 (98 mols) are added. At the completion of this reaction, 2024 grams of PrO (46 moles) are added and the reaction allowed to go to completion. The resulting polymer is a dark viscous fluid soluble in an aromatic solvent.

Example 5-A O For this example a conventional autoclave equipped to handle alkylene oxides is necessary. 946 grams of 5-A (N-400-I-3 moles lauric acid minus 3 moles H O) are charged into the autoclave. The charge is catalyzed with 100 grams of sodium methylate, purged with nitrogen and heated to 150 C. 480 grams (4 moles) of styrene oxide are added and reacted for 24 hours with agitation. The resulting product is a dark extremely viscous fluid.

Example 7A O For this example a conventional autoclave equipped to handle alkylene oxides is necessary. 1314 grams of 7-A (N-400-l-4 moles palmitic acid minus 6.2 moles H O) are charged into the autoclave. Following the addition of grams of sodium methylate and a nitrogen purge, the mass is heated to C. 660 grams of EtO (15 moles) are added and the reaction proceeded to completion. Then 1440 grams of BuO (20 mols) are added and again the reaction proceeded to completion. The resulting polymer is a dark viscous fluid soluble in an aromatic solvent.

TABLE III.-ACYLATED, OXYALKYLATED N-40O [Moles of oxide/mole oi reactant] EtO PrO BuO Ex. Physical Properties Moles Wgt. Moles Wgt Moles Wgt.

1A4Oi 42 (II) 1,048 78 (I) 4, 524 Dark, viscous liquid. 1-A402 8 (II) 352 (I) 3,422 Do. 1A4Oa 8 (III) 352 18 (II) 1 14404-- 23 (III) 1, 018 47 (I) 3AaO| 12 (I) 528 22 (II) 3AaOz.- 12 (II) 528 29 (I) 3AaO3 46 (II) 2,024 98 (I) 4AiOi.. 4 176 4Ai0g 4-AiOa 3 (I) 132 3 (II) 5Al0i-. 5A10g 2 (I) 116 3 (II) 216 Do. 5A1Oa Styrene oxide 4 moles, 480 grams Dark, viscous liquid: 5A1O4 Octylene oxide 5 moles, 635 grams Do. 7A1O1 (I) 660 (II) 1,440 Dark, thick liquid. 7-A10;- 10 (II) 440 (I) Do. 7-A1Oa 4, 796 210 (I) Do. 9-Aa0i l, 018 (II) D0. 9-A3Oz 1, 018 26 (II) Do. 9-Aa0a 1, 584 78 (I) Do. 11-14101--- 32 (I) 1, 408 23 (II) Solid. 11-At02. 13 (I) 572 49 (II) D0.

The following table presents specific illustration of compounds other than N-400 and its derivatives.

Example 2O A One mole of 2-0 (2894 grams) is mixed with one TABLE IIIA.ACYLATED, OXYALKYLATED BRANCHED mole of palmitic acid (256 grams) at room temperature. Vacuum is applied and the temperature is raised slowly until one mole of water (18 grams) is removed. This product is a dark viscous liquid.

Example 6-0 A POLYAMINES Mols of Oxide Per M01 of Beactant Example Physical Properties EtO PrO B110 5 Dark. viscous liquid. 10 (II) 60 (I) Do. Do. (111) (II) Do.

Styrene oxide, 4 mols 3 (I) Do. 12 (II) Do.

Octylene oxide, 5 mols 10 (I) 0 (I 10 (III) Do. (I) 2 (II) Do. 4 Do. 3 (II) 8 (I) I (III) Do. 15 Do. 3 Do. Do. 60 (II) 5 (III) 26 (I) Do. 1 Do. 5 Do. 3 Do.

Epoxide 201, 1 m Styrene oxide, 10 mols OXYALKYLATION THEN ACYLATION The prior oxyalkylated branched p'olyamines can be acylated with any of the acylation agents herein disclosed (in contrast to acylation prior to oxyalkylation). Since these reactants also have hydroxy group acylation, in addition to reaction with the amino groups noted above, also includes esterification.

The method of acylation in this instance is similar to that carried out with the polyamine itself, i.e., dehydration wherein the removal of water is a test of the completion of the reaction.

Example 1O A One mole of 1O (620 grams) is mixed with three moles of acetic acid (180 grams) and 400 ml. of xylene at room temperature. The temperature is raised slowly to l20130 C. and refluxed gently for one hour. The temperature is then raised to l-160 C. and heated until 3 moles of water and all of the xylene are stripped off. The dark product is water-soluble.

dark viscous liquid at room temperature.

Table IV contains examples which further illustrate the invention.

The symbol employed to designate oxy- 50 alkylated, acylated products is OA.

TABLE IV.OXYALKYLATED, THEN ACYLATED BRANCHED POLYAMINE N-400 Acylating agent Water removed Physical Ex. properties Moles oi Wgt., Wgt. Name acylating grams Moles (g) agent 3 180 3 54 Dark liquid. 1 282 1 18 Do. 2 568 2 36 Solid. 1 200 1 18 Dark liquid. 2 457 2 36 Do. 1 256.4 1 18 D0. 2 564 2 36 Solid. 4O A Ricinoleic 1 298.5 1 18 Dark liquid. 5-012. Abietic acid- 1 302.4 1 18 Dark solid. 5-O;A-- Talloil 1 175 1 18 Dark liquid. 6-O1A Lin0le1c 1 280.4 1 18 Do. e-oian 01am 2 564 2 36 Do.

6-O;A Maleic an- 1 98 1 18 Viscous hydride. liquid. 6-O5A- Diglycolic--- 1 134 1 18 Do. 7O1A- Lauric 2 400 2 36 Dark liquid. 801A Stearic 1 284 1 18 Solid.

The following table presents specific illustration of compounds other than N-400 and its derivatives.

TABLE IV-A.-OXYALKYLATED, THEN ACYLATED BRANCHED POLYAMINE Water Re- Mols of moved Physical Example Name Acylating Wt. in Proper- Agent Grams tics Mols Wt. in Grams Ill-03A-.- Stearic 1 284. 1 18 Solid. 11-0 11--- Lauric 2 400 2 36 Viscous liquid 110A Diglycolic.-- 1 134 1 18 Dark liquid. 12-0111- 1 98 Viscous liquid. 1301A Ole 2 564 1 18 Do. 14-02 1 280. 4 1 18 Do. 15-0111.-- 1 175 1 18 Do. 16-03 Abietic acid 1 302 1 18 Solid. 17-011-.-. Ricinoleic 1 298 1 18 Viscous liquid 2 .564 2 36 Do. 1 256 1 18 Solid. 2 457 2 36 D0. 1 200 1 18 Do. 2 568 2 36 Do. 1 282 1 18 Viscous liquid. 23-0211-.. Acetic 1 60 1 18 Do. 24-O2A Diphenolic. 1 286 1 18 130. 25O1A Terephl 166 1 18 Solid.

thalic. 25-0 4A. Naphthenic- 2 330 2 36 Viscous liquid. 25-O@A.- do 1 330 1.9 34 Do. 26-O1A Benzoic 1 122 1 18 Do. 26-0211--- Laurie 1 200 1. 8 32 Do.

HEAT TREATMENT OF OXYALKY'LATED PRODUCTS The oxyalkylated products described herein, for example, those shown in Table II relating to oxyalkylated branched polyamines and those in Table III relating to oxyalkylated, prior acylated, branched polyamines can be heat treated to form useful compositions.

In general, the heat treatment is carried out at 200- 250 C. Under dehydrating conditions, where reduced pressure and a fast flow of nitrogen is used, lower temperatures can be employed, for example 150200 C.

Water is removed during the reaction, such as by means of a side trap. Nitrogen passing through the reaction mixture and/or reduced pressure can be used to facilitate water removal.

The exact compositions cannot be depicted by the usual chemical formulas for the reason that the structures are subject to a wide variation.

The heat treatment is believed to result in the polymerization of these compounds and is effected by heating same at elevated temperatures, generally in the neighborhood of 200-270 C., preferably in the presence of catalysts, such as sodium hydroxide, potassium hydroxide, sodium ethylate, sodium glycerate, or catalysts of the kind commonly employed in the manufacture of superglycerinated fats, calcium chloride, iron and the like. The proportion of catalyst employed may vary from slightly less than 0.1%, in some instances, to over 1% in other instances.

Conditions must be such as to permit the removal of Water formed during the process. At times the process can be conducted most readily by permitting part of the volatile constituents to distill, and subsequently subjecting the vapors to condensation. The condensed volatile distillate usually contains water formed by reaction. The water can be separated from such condensed distillate by any suitable means, for instance, distilling with xylene, so as to carry over the water, and subsequently removing the xylene. The dried condensate is then returned to the reaction chamber for further use. In some instances, condensation can best be conducted in the presence of a high-boiling solvent, which is permitted to distill in such a manner as to remove the water of reaction. In any event, the speed of reaction and the character of the polymerized product depend not only upon the orginal reactants themselves, but also on the nature and amount of catalyst employed, on the temperature employed, the time of reaction, and the speed of water removal, i.e., the effectiveness with which the water of reaction is removed from the combining mass. Polymerization can be effected without the use of catalysts in some instances, but such procedure is generally undesirable, due to the fact that the reaction takes a prolonged period of time, and usually a significantly higher temperature. The use of catalyst such as iron, etc. fosters the reaction.

The following examples are presented to illustrate heat treatment. The symbol used to designate a heat treated oxyalkylated polyamine is OH and an acylated, oxyalkylated product is AOH. In all examples 500 grams of starting material and a temperature of 225-250 C. are employed.

Example 1-O H A conventional glass resin vessel equipped with a stirrer and water trap is used. Five hundred grams of 1O are charged into the above resin vessel along with five grams of CaCl The temperature is raised to 225250 C. and heated until 50 grams of water (2.8 mols) are evolved. This process takes 7.5 hours of heating. The product is an extremely viscous material at room temperature. However, upon warming slightly this product dissolves easily in water.

Example 2-O H The process of the immediately previous example is repeated using 2-0;, but substituting sodium methylate for calcium chloride. The product is a dark, viscous, water-soluble material.

Example 6O H The process of Example 1O H is repeated using 6-0 but substituting powdered iron for calcium chloride.

TABLE V.HEAT TREATED (1) OXYALKYLATED AND (2) ACYLATED, OXYALKYLATED POLYAMINE N-400 Water Removed Ex. Catalyst, Time in 5 grams Hours Wgt. Moles 63 3. 5 8. 0 56 3. 1 9. 3 40 2. 2 10.0 31 1. 7 7. 5 61 3. 4 8. 0 33 l. 8 6.8 63 3. 5 8. 0 3A O1H..-. 47 2. 6 8. 5

7A1O2H NaOH 27 1. 5 7. 5 9AaO3H- 50 2. 8 8.0 11-A1O1H.--- 54 3.0 8. 5

All of the above products are dark, viscous liquids.

The following table presents specific illustration of compounds other than N-400 and its derivatives.

TABLE VA.HEAI TREATED (1) OXYALKYLATED AND (2) ACYLATED, OXYALKYLATED BRANCHED IOLYAMINE Example Catalyst Wt. of Water Mols of H Time in grams) Removed Removed Hours 50 2. 8 8. 0 54 3. 0 8. 5 40 2. 2 10. 0 56 3. l 9.3 63 3. 5 8.0 58 3. 2 7. 5 29 1. (i 8. 5 50 2. 8 7. 5 29 l. 6 8. 5 264110211.-. 63 3. 5 8.0 27-A1O3H." 33 1. 8 6. 8 3lA1O2H. 27 1. 5 7. 5 33-.A1O1H--. 50 2. 8 8.0

All of the above products are dark, viscous liquids.

ALKYLATION Alkylation relates to the reaction of the branched polyamine and derivatives thereof with alkylating agents.

Any hydrocarbon halide, e.g. alkyl, alkenyl, cycloalkenyl, aralkyl, etc., halide which contains at least one carbon atom and up to about thirty carbon atoms or more per molecule can be employed to alkylate the products of this invention. It is especially preferred to use alkyl halides having between about one to about eighteen carbon atoms per molecule. The halogen portion of the alkyl halide reactant molecule can be any halogen atom, i.e., chlorine, bromine, fluorine, and iodine. In practice, the alkyl bromides and chlorides are used, due to their greater commercial availability. Non-limiting examples of the alkyl halide reactant are methyl chloride; ethyl chloride; propyl chloride; n-butyl chloride; sec-butyl iodide; t-butyl fluoride; n-amyl bromide; isoamyl chloride; n-hexyl bromide; n-hexyl iodide; heptyl fluoride; 2-ethylhexyl chloride; n-octyl bromide; decyl iodide; dodecyl bromide; 7-ethyl-2-methyl-undecyl iodide; tetradecyl bromide; hexadecyl bromide; hexadecyl fluoride; heptadecyl chloride; octadecyl bromide; docosyl chloride; tetracosyl iodide; hexacosyl bromide; octacosyl chloride; and triacontyl chloride. In addition, alkenyl halides can also be employed, for example, the alkenyl halides corresponding to the above examples. In addition, the halide may contain other elements besides carbon and hydrogen as, for example, where dichloroethylether is employed.

The alkyl halides can be chemically pure compounds or of commercial purity. Mixtures of alkyl halides, hav ing carbon chain lengths falling within the range specified hereinbefore, can also be used. Examples of such mixtures are mono-chlorinated wax and mono-chlorinated kerosene. Complete instructions for the preparation of mono-chlorowax have been set forth in United States Patent 2,238,790.

Since the reaction between the alkyl halide reactant and the branched polyamine is a condensation reaction, or an alkylation reaction, characterized by the elimination of hydrogen halide, the general conditions for such reactions are applicable herein. It is preferable to carry out the reaction at temperatures of between about 100 and about 250 C., preferably between about 140 C. and about 200 C., in the presence of a basic material which is capable of reacting with the hydrogen halide to remove it. Such basic materials are, for example, sodium bicarbonate, sodium carbonate, pyridine, tertiary alkyl amines, alkali or alkaline earth metal hydroxides, and the like.

It is preferred to perform the reaction between the alkyl halide reactant and the branched polyamine reactant in a hydrocarbon solvent under reflux conditions. The aromatic hydrocarbon solvents of the benzene series 20 are especially preferable. Non-limiting examples of the preferred solvent are benzene, toluene, and xylene. The amount of solvent used is a variable and non-critical factor. It is dependent on the size of the reaction vessel and on the reaction temperature selected. For example, it will be apparent that the amount of solvent used can be so great that the reaction temperature is lowered thereby.

The time of reaction between the alkyl halide reactant and the branched polyamine is dependent on the weight of the charge, the reaction temperature selected, and the means employed for removing the hydrogen halide from the reaction mixture. In practice, the reaction is continued until no more hydrogen halide is formed. In general, the time of reaction will vary widely such as between about four and about ten hours.

It can be postulated that the reaction between the alkyl halide reactant and the branched polyamine results in the formation of products where the alkyl group of the alkyl halide has replaced a hydrogen atom attached to a nitrogen atom. It is also conceivable that alkylation of an alkylene group of the branched polyamine can occur. However, the exact composition of any given reaction product cannot be predicted. For example, when two moles of butyl bromide are reacted with one mole of Polyamine N-400, a mixture of mono-, diand triand higher N-alkylated products can be produced. Likewise, the alkyl groups can be substituted on different nitrogen atoms in different molecules of the branched polyamine.

Thus, the term Alkylation as employed herein and in the claims includes alkenylation, cycloalkenylation, aralkylation, etc., and other hydrocarbonylation as well as alkylation itself.

In general, the following examples are prepared by reacting the alkyl halide with the branched polyamine at the desired ratio in the presence of one equivalent of base for each equivalent HCl given ofl during the reaction. Water formed during the reaction is removed by distillation. Where the presence of the anions, such as chlorine, bromine, etc., is not material and salts and quaternary compounds are desired, no base is added.

The following examples are presented to illustrate the alkylation of the branched polyamines.

Example 5-K One mole of each of the following: tetradecylchloride, Polyamine N400, and sodium bicarbonate are placed in a reaction vessel equipped with a mechanical stirrer, a thermometer and a condenser reflux take-off for removal of water from the reaction as it is evolved in an az/eotropic mixture of water and a hydrocarbon solvent. The reflux take-ofl is filled with xylene. The stirred reactants are heated to about C. whereupon an exothermic reaction causes the temperature to rise to about C. The reaction temperature is then increased to 160 C. and held there for two hours. Then, xylene is added to the reaction vessel in an amount suflicient to cause a xylene reflux to take place at a temperature of -170 C. The reaction is continued for six hours or until the theoretical amount of water is removed. Thereupon, an equal volume of xylene is added to the reaction mixture and the resultant solution is filtered. This filtrate is then evaporated under reduced pressure to yield a dark amber oil. No halogen was present in this product as evidenced by a negative Beilstein copper wire test.

Example 5K X The above reaction is repeated except that no sodium bicarbonate is employed in the reaction. The reaction product contained chlorine.

The reactions shown in the following table are carried out in a similar manner. Each reaction in the table is carried out in two ways( 1) in the presence of base as in 5-K to yield the halogen-free alkylation product Table VI and (2) in the absence of base to yield halogen con,- taining products in the manner of SK X Table VII.

The alkylated products of this invention contain pri- TABLE vr c n mary, secondary, tertiary, and quaternary amino groups. By controlling the amount of alkylation agent employed Ratio, Moles of Alkyl- Physical and the conditions of reaction, etc., one can control the iiifit l iil iir n iii e i iih i s type and amount of alkylation. For example, by reaction Derivatives less than the stoichiometric amount of alkylation agent one could preserve the presence of nitrogen-bonded hydro- 3-K1 2-ethyl-hexyl chlo- 3:1 Vicous gen present on the molecule and by exhaustive alkylation in the presence of sufficient basic material, one can form do 7:1 130. more highly alkylated compounds. P 2:1 f The moles of al kylating agent reacted with the branched -K: --do 3:1 Do. polyamine will depend on the number of alkylation reacif 'gz fifiggfigjj S315: tive positions contained therein as well as the number of q d. moles of alkylating agent one wishes to incorporate into IIgSIIIIIIII: j the molecule. Theoretically every hydrogen bonded to a Octadecyl chloride--- 1:1 Sem1i -d nitrogen atom can be alkylated. We have advantageously HQ 3:1 reacted 1l0 moles of alkylatmg agent per moles of Polydo 4:1 V. Do. amine N400, but preferably 1-6 moles. With Polyamine Benzyl emonde m N-SOO and N-1200, twice and three times as many moles 7-K2 --do 5:1 1% of alkylating agent can be employed respectively, i.e., with fik gg j 3,- Polyamine N-8 OO, l-ZO moles, preferably 1l-2; with d Polyamine N-1200, l-3O but preferably l-'18. Optimum "jjjjdgjjjjjjjjjjjjjjjj Z; alkylation will depend on the particular application. Dodgcenyl chloride- 1: S D In addition, the alkyl halide may contain functional 23 groups. For example, chloroacetic acid can be reacted 25 3 55 S with the branched polyamines to yield a compound con- 2,5? e o 1 taining carboxylic acid groups 2 "g8 g 38- PN CH2CQOH ildichlo robdten efi: 1Z2 vilsicou s i qui wherein P is the residue of the olyamine. "IggIIIIIIII: 23; In addition, the branched polyamine can be alkylated 1,4;xylylene dichlo- 1:2 Do. with analkyl halide such as alkyl chloride and then rejg DO, acted with chloroacetic acid to yield an alkylated poly- 5: 3 amine containing carboxylic acid groups {{ff ggffff jfffff jf f; 31

0 (1 5:1 Semisolid. (C 12H21s-N) n P (CHZC OH) is 1 itiihgid The symbol employed to designate an al kylated poly- 5 q amine is K. Where the product is a salt or a quaternary Ethylene dichloride ggg the symbol is 5-O1AK l,4-dich10robutene-2 4:1 130.

TABLE VI.-ALKYLATED PRODUCTS 40 P114011? DodeQylchloride-u l- S0 1 Ratio Moles ofAlkyl Physical 7AiO1K n-Amylbromide 4:1 Vificous1 qui Ex. Allgi ag ns gg 4-OzHK re iment: dichlo- 3:1 Do.

min [1 Derivativ 6-O HK Methyl chloride 6:1 Liquid. 7-A102HK- Dichlorodiethylether. 4:1 vilsicousl Ill 1-K1 Butyl chloride 1:1 Vi s go l s 1141 0 1115 do 4:1 in. 1-Kz do 3:1 Do.- l-m dn 5:1 Do. 31%: 1 bmmidem" B3: The following table presents specific illustration of compounds other than N400 and its derivatives.

TABLE VIA.ALKYLATED PRODUCTS Ratio, Mols of Branched Alkylating Agent Per Physical Example Polyamine Alkylating Agent Mol of Branched Prop- Polyamine or erties Derivatives 14-K1 N-800 Benzyl chloride 2:1 Viscous liquid. 3:1 Do. 521 D0. 1:1 Semisolid. -d0 3:1 D0. Allyl chloride 1:1 Viscous liquid. do 2:1 Do. do 3:1 Do. Butyl chloride 1:1 Do. (1 3:1 Do. i -do 5:1 Do. Methyl chloride 6:1 D0. n-Amyl bromide 3:1 D0. Dodecenyl chloride. 1:1 Do. Dimethyl sulfate 2:1 Do. Dichlorodiethylether. 1: 1 D o. Allyl chloride 2:1 D0. Octadecyl chloride. 3:1 Do. nbromide.-- 1:1 Do. Benzyl chloride 2:1 D0. Dichl0ropentane 1:1 D0. 25A O HK Methyl chloride 1:1 Do.

TABLE VIL-SALT AND QUATERNARY PRODUCTS OF ALKYLATED N-400 AND DERIVATIVES Alkylating Agent 3K1X 2-cthyl-hexy1 chloride.

3-K2X -dO -do Dodeeyl chlorid Benzylchlorideride. Methyl chloride--- Methyl chloride Dimcthylsulfete Ethylene dichloride- 1 Adiehlorbuteue-l Dodccyl chloride n-Amy1bromide 1,4- xylylene dichlo- D ichlorodiethylether. do

Physical Properties viscous TABLE VIIA.SALT AND QUATERNARY PRODUCTS OF liquid ALKYLATED BRANCHED POLYAMINE AND DERIVA- TIV ES D0. Do. Ratio of Alkylatmg Physical Do. Example Alkylating Agent Agent/0t Polyamine Proper- Do. or Derivative tics Do. Do. Ethylene dichloride. 2: 1 Solid. Semin-Amyl bromide 3:1 Do. solid. Dichlorodiethyl- 4:1 Do. Solid. ether.

Do. Dimethyl sulfate--. 3:1 Do. Serni- Methyl chloride".-. 2:1 Do. solid. 1,4-xylene dichlo- 6:1 Do. Solid. ride.

Do. Dodecylbenzyl 8:1 Semi- Do. 0 ride. solid. Do. 1,4-dichlorobutene-2. 3:1 Do. Do. Benzyl chloride"..- 4:1 D0. Semi- Methyl chloride 3:1 Do. solid. Ethylene dichloride. 2:1 Do. Do. Dodecyl cl1loride 1:1 0. Do. Dichlorodiethyl- 1 :1 Solid. Viscous 2 ether.

liquid. 10-O3KX Benzyl chloride".-. 3:1 Do. Do. 11-O4KX -.do 2:1 Do. Do. -O5KX d0 1:1 Do, Semizfi-ArOzKXnn Methyl chloride 5:1 Do. solid. d 4:1 D0. Solid. 3:1 Do. Do. 3:1 Do. Do. ether.

14OZHKX do 2:1 Do. Do. 25-A1OzHKX. .do 1:1 Do. Do. Viscous liquid.

I13o. 0. Do.

Do. 38 ALKYLATED IH EN ACYLATION 5mm The alkylated material prepared above can be further d. 40 treated with acylating agent where residual acylatable amino groups are still present on the molecule. The acyla- Li 33- tion procedure is essentially that described above wherein g carboxylic acids react with the alkylated polyamine under gg dehydrating conditions to form amides and cyclic amidines. The product depends on the ratio of moles of water reg moved for each carboxylic acid group, i.e., 1 mole water/ viscou's 1 mole carboxylic essentially amides; more than 1 mole liquid water/1 mole carboxylic acid group, essentially cyclic amidines, such as imrdazolines. g Such compounds are illustrated in the following table. Solid, The symbol employed to designated alkylated acylated products is KA and acylated, alkylated, acylated products is AKA.

TABLE VIII..ACYLA'IED PRIOR ALKYLATED BRANCHED POLYAMINES Moles of Aeylat- Moles Ex. Acylatmg Agent mg Agent/Mole Wgt. Water Physical oi N 400 or Removed Properties Derivative 2 564 3. 1 Viscous liquid. 3 852 3.0 Solid. 2 400 2. 8 Viscous liquid. 3 769 4.1 Do. 1 600 2. 2 Do. Alkenyl (C1z) 1 266 0. 5 Solid.

succuuc anhydrlde.

1 282 1. 7 Viscous liquid. 2 564 3. 1 Do. 2 400 2. 8 Do. 2 598 3. 0 Do. 0 1 282 1. 5 Do. 3-A3KA]... A1kenyl (0n) l 266 SOlid.

succmic anhydride. 3A3KA2. Oleic 1 282 1. 5 Viscous liquid.

The following table presents specific illustration of compounds other than N-400 and its derivatives.

free, to eliminate undesirable side reactions. At room temperature, slowly add 53 grams of acrylonitrile (1 mol) TABLE VIII-A.ACYLATED, PRIOR ALKYLATED BRANCHED POLYAMINE Mols of Acylating Wt. of Mols of Physical Example Acylating Agent Agent/M01 of Acylating Water Proper- Polyamine or Agent Removed ties Derivative Used 14-K1A Laurie 1 200 1. 1 Solid. 154? A Rininnleio 3 894 3. U DO. 16- A 2 564 3. D0. 17-K1A 2 512 2. 0 Do. 18-A7KA 1 568 1. 0 Do. -O3KA 1 282 1. 0 D0. OoKA 2 560 2. 0 D0. 26-A OflTA 1 60 1. 5 DO. 11OzAKA Dlglycollc 1 134 1. 0 D0. 14-0 zHKA. Maleic anhydride. 2 196 Do. 25-A101HKA Olelc 1 282 1. 5 D0.

OLEFINATION 25 The reaction proceeds smoothly without the aid of a (Olefination relates to the reaction of the polyamine and derivatives with olefins) unsaturated compounds, particularly compounds containing activated double bonds, so as to add the polyamine across the double bonds as illustrated herein:

Where the compound contains an additional active hydrogen, other unsaturated molecules can be added to the original molecule for example:

Where one or more active hydrogens are present at another reactive site, the following reaction could take place:

The reaction is carried out in the conventional manner such as illustrated, for example, in Synthetic Organic Chemistry, Wagner and Zook (Wiley, 1953), page 673.

Non-limiting examples of unsaturated compounds which can be reacted with the polyamine and derivatives thereof including the followingacrylonitri1e, acrylic and methacrylic acids and esters, crotonic acid and esters, cinnarnic acid and esters, styrene, styrene derivatives and related compounds, butadiene, vinyl ethers, vinyl ketones, maleic esters, vinyl sulfones, etc.

In addition, the polyamine and derivative thereof containing active hydrogens can be used to prepare telomers of polymer prepared from vinyl monomers.

The following are examples of olefination. The symbol employed to designate olefination is U and alkylation, olefination KU.

Example 1-U The olefination reaction is carried out in the usual glass resin apparatus. Since the reaction is that of a double bond with an active hydrogen, no Water is eliminated. The reaction is relatively simple, as shown by the following example:

Charge 400 grams of N-400 (1 mol) into glass resin apparatus. Care should be taken that the N-400 is watercatalyst. Warm gently to -100 C. and stir for one hour.

Example 6-U To 800 grams of N-400 (2 mols) in 800 grams of xylene, add 124 grams of divinyl sulfone (1 mole) at room temperature. This reaction is exothermic and care must be taken to prevent an excessive rise in temperature which would cause cross-linking and insolubilization.

Example 3O U Same reactions as Example 1-U except that 1 mol of methyl acrylate is substituted for acrylonitrile and 3-O is substituted for the N-400. Part of this product is thereupon saponified with sodium hydroxide to form the fatty amino acid salt.

Further examples of the reaction are summarized in the following table:

TABLE IX.OLEFINATION Moles of Olefin] Compound Olefin Mole of Polyamine Time Tempera- N-400 or Polyamine ture, O.

N400 Derivative Aerylonitrile 1/1 1 hr- 80-100 Methyl meth- 1/1 1 hr 80-100 acrylate. do 3/1 1 hr 80-100 Ethyl cinna- 1/1 2 hrs--. 120

mate. Ethyl crotonate. 1/1 2 hrs. 120 Di-ctyl male- 1/1 2 hrs 150 a e. Divinyl sulfone. 1/2 30 min. Styrene- 1/1 30 min 90 0.--- 3/1 30 min 90 Lauryl meth- 3/1 1 hr- 120 aerylate. Divinyl sulfone. 1/2 30 min- 90 4A3U1 Methyl meth- 1/1 1 hr acrylate. 4-A3Uz Divinyl sulfone. 1/2 30 min. 90 6-K1 Acrylonitrile 2/1 1 hr- 70 1/1 1 hr 90 1/1 1 hr 90 1/1 1 hr 90 1/1 1 hr- 90 1/1 1 hr. 90 1/1 1 hr 90 ill 1 hr-.." 90

TABLE IXA.OLEFINATION Schifis base is present on the branched amino group rather than on the terminal amino group, etc.

Mols of Olefin/M01 Branched of Branched Poly- Temp., Example Polyamine Olefin amine or Branched Time C.

Poly amine Derivative Acrylonitrile 1:1 1 hr 80-100 Styrene 1:1 1 hr 80-100 Divinyl sulfone 1 1 1 hr- 80-100 Di-oetylmaleate 1: 1 1 hr. 125 Acrylonitrile 2:1 30 min- 80-100 Methylacrylatel :1 30 min 80-100 Ethyl crotonate... 2:1 30 min 120 Divinyl sulfone 2: 1 30 min- 120 Ethyl cinnarnate 1:1 2 hrs 120 Di-octyl maleate. 1: 1 2 hrs. 120 Methyl meth- 1:1 1 hr. 100

aerylate. Styrene 2:1 1 hr. 100 Aorylonitrile 2:1 1 hr- 100 Ethyl cinnamate" 1:1 1 hr. 110 Ethyl crotonate-.. 1 1 2 hrs. 120 25O1AU Dlvinyl sulfone... 2:1 1 hr 80 12-O1HU. Lauryl meth- 3: 1 2 hrs- 130 aerylate. 25-A|OZHU Acrylonitrlle 1:1 1 hr 90 16-K3HX Dlvinyl sulfone 1: 1 1 hr- -K1U 4:1 1 hr- 90 33-ArOiKU 2:1 1 hr 90 -A1O3HKU-- 1:1 1 90 CARBONYLATION (Carbonylation relates to the reaction of the branched polyamine and derivatives with aldehydes and ketones) Where primary amino groups are present on the polyamine reactants, Schiffs bases can be formed on reaction with carbonyl compounds. For example, where an aldehyde such as salicylaldehyde is reacted with Polyamine N-400 in a ratio of 3 moles of aldehyde to 1 mole of polyamine, the following type of compound could be formed:

HO OH and other isomeric configurations, such as where the A wide variety of aldehyde may be employed such as aliphatic, aromatic, cycloaliphatic, heterocyclic, etc., including substituted derivatives such as those containing aryloxy, halogen, heterocyclic, amino, nitro, cyano, carboxyl, etc. groups thereof. Non-limiting examples are the following:

A ldehydes Benzaldehyde 2-methylbenzaldehyde 3-methylbenzaldehyde 4-methylbenzaldehyde 2-methoxybenzaldehyde 4-methoxybenzaldehyde a-naphthaldehyde b-naphthaldehyde 4-phenylbenzaldehyde Propionaldehyde n-Butyraldehyde Heptaldehyde Aldol Z-hydroxybenzaldehyde 2-hydroxy-6-methylbenzaldehyde 2-hydroxy-3 -methoxybenzaldehyde 2-4-dihydroxybenzaldehyde 2-6-dihydroxybenzaldehyde Z-hydrOXynaphthaIdehyde-I 1-hydroxynaphthaldehyde-2 Anthrol-Z-aldehyde-l Z-hydroxyflucreme-aldehyde-1 4-hydroxydiphenyl-aldehyde-3 3-hydroxyphenanthrene-aldehyde-4 1-3-dihydroxy-2-4-dialdehydebenzene 2-hydroxy-5-chlorobenzaldehyde 2-hydroxy-3 5dibromobenzaldehyde Z-hydroxy-3-nitrobenzaldehyde 2-hydroxy-3-cyanobenzaldehyde 2-hydroXy-3 -carboxybenzaldehyde 4-hydroxypyridine-aldehyde-3 4-hydroxyquinoline-aldehyde-3 7 -hydroxyquinoline-aldehyde-8 Formaldehyde Glyoxal Glyceraldehyde Schiffs bases are prepared with the polyamines of this invention in a conventional manner such as described in Synthetic Organic Chemistry by Wagner and Zook (1953, Wiley), pages 728-9.

Where more extreme conditions are employed, the products may be more complex wherein the carbonyl reactant instead of reacting intramolecularly in the case of Schitfs base may react intermolecularly so as to act as a bridging means between two or more polyamino compounds, thus increasing the molecular weight of the polyamine as schematically shown below in the case where fiormaldehyde is the carbonyl compound:

In addition to increasing the molecular weight by means of aldehydes, these compounds result in the formation of cyclic compounds. Probably both molecular weight increase and cyclization occur during the reaction.

The following examples illustrate the reaction of carbonyl compounds with branched polyamines. The symbol employed to designate carbonylation is C, acylation, carbonylation AC, and alkylation, carbonylation KC.7

Example 1C Charge 400 grams of N400 and 400 grams of xylene into a conventional glass resin apparatus fitted with a stirrer, thermometer and side-arm trap. Raise temperature to 120 C. and slowly add 122 grams of salicylaldehyde (1 mol). Hold at this temperature for 2 hours. Vacuum is then applied until all xylene is stripped off. The reaction mass is a thick dark liquid which is soluble in water.

Example 6-C Using the same apparatus as above, charge 400 grams of N400. While stirring, add slowly at room temperature 82 grams of 37% aqueous formaldehyde (1 mol of HCHO). This reaction is exothermic and the temperature must be controlled with an ice bath. After the exothermic reaction has ceased, raise temperature to 100 C. The reaction mass may be stopped at this point. It is a viscous water-soluble material. However, it is possible to continue heating under vacuum until all of the Water has been eliminated. Cross-linking occurs with this procedure and care must be taken to prevent insolubilization.

Further examples of this reaction are summarized in the following table:

TABLE X.CARBONYLATION Compound Aldehyde Mol. Temp., Time Ratio O.

1-G1 Salieylaldehyde 1/1 120 2 hrs. l-Cz do 2/1 120 2 hrs. 1-03 do 3/1 120 2 hrs. 2-01 2-hydroxy-3-methoxy- 1/1 130 4 hrs.

benzaldehyde.

d 2/1 130 4 hrsv 3/1 130 4 hrs. /1 130 4 hrs.

3/1 110 1 hr. 3/1 90 2 hrs. 3/1 130 5 hrs. 3/1 2 hrs.

2/1 100 1 hr. 2/1 135 3 hrs.

2/1 150 1 hr. 1/1 120 2 hrs. 1/1 120 2 hrs. 1/1 120 2 hrs. 2/1 120 2 hrs.

1 Start 25 0., raise to 100 C.

The following table presents specific illustration of compounds other than N-400 and its derivatives.

TABLE XA.CARBONYLATION Compound Branched Aldehyde Mol. Temp, Time Polyamine Ratio C.

Formaldehyde 2:1 1 hour do 1:1 80 Do.

do 0. 5:1 80 Do.

Acetaldehyde 2: 1 D 0.

do 1:1 100 Do.

do 0. 5:1 100 Do.

do 2:1 Do.

- -do 1:1 120 D0.

Benzaldehyde..- 3:1 110 Do.

do 2:1 110 Do.

do 1:1 110 D0.

Glyoxal 1:1 105 Do.

do 0. 5:1 105 Do.

do 0.25:1 105 D0.

Glyceraldehyde. 1:1 2hours l1UaC- 1:1 80 1 hour 12-01HUC o 05:1 80 Do.

The examples presented above are non-limiting examples. It should be clearly understood that various other combinations, order of reactions, reaction ratios, multiplicity of additions, etc. can be employed. Where additional reactive groups are still present on the molecule, the reaction can be repeated with either the original reactant or another reactant.

The type of compound prepared is evident from the letters assigned to the examples. Thus, taking the branched polyamine as the starting material, the following example designations have the following meaning:

Example designation: Meaning (1) A Acylated. (2) A0 Acylated, then oxyalkylated. (3) AOA Acylated, then oxyalkylated,

then acrylated. (4) AOH Acylated, then oxyalkylated,

then heat treated. (5) AX Salt or quaternary of (l). (6) AOX Salt or quaternary of (2). (7) AOAX Salt or quaternary of (3). (8) AOHX Salt or quaternary of (4). (9) O Oxyalkylated. (10) 0A Oxyalkylated, then acylated. (11) OH oxyalkylated, then heat treated. (12) K Alkylated. (13) KX Salt or quaternary of (12). (14) KA Alkylated, then acylated. (15) AK Acylated, then alkylated. (16) AKX Salt or quaternary of (15). (17) OK oxyalkylated, then alkylated. (18) OKX Salt or quaternary of (17). (19) C Carbonylated. (20) AC Acylated, then carbonylated. (21) KC Alkylated, then carbonylated. (22) CO Carbonylated, then oxyalkylated. (23) U Olefinated. (24) AU Acylated, then olefinated. (25) KU Alkylated, then olefinated. (26) KUX Salt or quaternary of (25).

USE AS A CHELATING AGENT This phase of the invention relates to the use of the compounds of our invention as chelating agents and to the chelates thus formed.

Chelation is a term applied to designate cyclic structures arising from the combination of metallic atoms with organic or inorganic molecules or ions. Chelates are very important industrially because one of the unusual features of the chelate ring compounds is their unusual stability in which respect they resemble the aromatic rings of organic chemistry. Because of the great atfinity of chelating compounds for metals and because of the great stability of the chelates they form, they are very important industrially.

The compositions of this invention are excellent chelating agents. They are particularly suitable for forming chelates of great stability with a wide variety of metals.

Chelating metals comprise magnesium, aluminum, arsenic, antimony, chromium, iron, cobalt, nickel, palladium, and platinum. Particularly preferred of such metals as chelate constituents are iron, nickel, copper and cobalt.

The chelates formed from the compositions of our invention are useful as bactericidal and fungicidal agents, particularly in the case of the copper chelates. In addition the chelates can be employed to stabilize hydrocarbon oils against the deleterious effects of oxidation.

In general, these chelates are prepared by adding a suffi cient amount of a metal salt to combine with a compound of this invention. They are prepared by the gen eral method described in detail by Hunter and Marriott in the Journal of the Chemical Society (London), 1937, 2000, which relates to the formation of chelates from metal ions and salicylidene imines.

The following examples are illustrative of the preparation of the chelates.

Example 8-A To a solution of 0.1 mole of the chelating agent of Example 8A in alcohol is added 0.1 mole of cupric acetate monohydrate. After most of the alcohol is evaporated, a green solid precipitates which analysis indicates to be the copper chelate.

Example 6-K The above procedure is used except the cobaltous acetate tetrahydrate is employed to yield a red solid which analysis indicates to be the cobaltous chelate.

Example 4A C The above procedure is used except that nickelous acetate, Ni(OAC) .4H O is employed. A dark green product is formed.

To save repetitive detail, chelates are formed from the above nickel, cobalt and copper salts, and the compounds shown in the following table.

CHELATING AGENTS 32 tiveness of foam-destroying agents are difficult to predict.

Our novel process of reducing or destroying foams and of preventing their formation appears to be relatively general in applicability, in that it may be used with compositions comprising aqueous materials or solutions, compositions comprising nonaqueous materials, such as hydrocarbon liquids, and compositions comprising mixtures of aqueous and nonaqueous media. Our process consists in subjecting a foaming or potentially-foaming composition to the action of a small proportion of the reagents of this invention as anti-foamers, thereby causing the foaming properties of the liquid to be diminished, suppressed or destroyed. In applying our process to the reduction or destruction of a foam, the reagent is poured or sprayed or dripped into the body of foam on top the liquid, as desired; and the foam breaks and is destroyed or reduced, substantially at once, as a consequence of such addition of said reagent. Adding the reagent to the liquid underlying such already-formed foam is also practicable. In applying our process to the prevention of foaming, the reagent is admixed, in some small proportion, with a potentially-foaming liquid, by any desired or suitable procedure. The ability of the system to foam is destroyed or at least materially reduced by such addition of said reagent.

It is usually convenient to dilute our reagents during manufacture or before use with some suitable solvent. Solvents generally suitable for incorporation into our reagent include: water; petroleum hydrocarbons, like gasoline, kerosene, stove oil, aromatic solvent; coal tar products, such as benzene, toluene, xylene, tar acid oil, cresol, anthracene oil; alcohols, particularly aliphatic alcohols like methyl, ethyl, isopropyl, butyl, hexyl, octyl, etc. Miscellaneous solvents, such as pipe oil, carbon tetrachloride, etc., may be employed. Sometimes other factors such as whether it imparts an objectionable odor to the defoamed composition or to the products into which it finds its way will determine the choice of solvent. In general, the amount of finished anti-foamer reagent employed is so small that considerable tolerance of undesirable properties in a solvent exists.

The mixture of active ingredient and solvent is stirred =until homogeneous. We prefer to employ a petroleum distillate in the proportion of 25 to 30% of the finished product, by volume, although water is an excellent solvent in some instances.

We desire to point out that the superiority of the reagent contemplated by our process is based upon its ability to reduce or destroy foam, or to prevent foam formation, in certain foaming or potentially foaming compositions more advantageously and at lower cost than is possible with other reagents or processes. Our reagents are useful in controlling foams in many different types of systems, aqueous and non-aqueous. They will control foams encountered in the manufacture of alkaline hypochlorite bleaches. They are effective in controlling foam in petroleum production and refining operations. They are effective in inhibiting foam in a gas-treating system, in which a mixture of glycols and alkanolamines is used to dehydrate and purify natural gas.

We can apply our reagents to the control of foam in protein adhesives solutions, such as casein and soybean adhesives, as used in the plywood industry, in papermaking, latex adhesives, printing inks, aqueous emulsion paints, which all produce foams which are amenable to our reagents.

In the foregoing description we have made it clear that our reagents may be used to reduce, destroy, or prevent foam. In the appended claims we have used the Word inhibit to include all these corrective and preventive aspects of our process and reagents.

The procedures employed in practicing our process are numerous. The following description will illustrate several techniques commonly employed. It should be understood that the claims are not limited to the procedures described, and that our process consists broadly in bringing into contact by any suitable means our reagent and the foam or the potentially foaming composition. 1

In controlling foam in a glycol-amine gas treating plant handling natural gas, the glycol-amine mixture has a volume of about 2,000 gallons and make-up is about 2,000 gallons a month. The reagents are injected into the liquid mixture in the return line from the stripping operation, by means of an electrically-powered proportioning pump of conventional design. The feed rate is less than 1 quart daily. Foam difiiculties in the system are satisfactorily controlled by this procedure.

In sewage plants, for example, in activated sludgeprocess plants, foam is frequently .a serious problem in aeration basins and elsewhere. In one such plant, our reagents will control foam when sprayed into the head of foam, or when sprayed into or simply poured into the liquid in such basins. The foam-inhibiting effect appears to persist quite satisfactorily.

Determination of the optimum or minimum amount of our foam-inhibiting reagents to be used in any application is accomplished in different ways. Small portions of the potentially foaming liquid are added to test bottles, different small proportions of our reagent added, and the chemicalized samples shaken for a short time. Simple observation of the relative speed and completeness of foam destruction should permit selection of the best reagent proportion to be applied on the large scale. The easiest way to determine the amount of reagent required is to introduce it into the foaming or potentially foaming liquid in a fairly large proportion, e.g., 1%, and then to reduce the reagent feed rate until foam destruction is just being accomplished satisfactorily. Usually foam destruction is directly proportional to the amount of reagent used, at least up to about 1% of reagent. In a few instances, it may be found that using more or less reagent than an optimum proportion will give inferior results.

If the proportions of reagents to be employed in the above test are very small, it may be desirable to determine the optimum proportions of foaming composition and anti-foamer by introducing the latter into the sample of foaming liquid in the form of a solution in a suitable solvent.

Our process is equally applicable to systems in which a foam is already in existence and to systems which are potentially foaming composition, in that they have the property of producing foams when agitated or mixed with air or some other suitable gas. Destruction, reduction and prevention are substantially equivalent actions. It is impossible to determine whether the reagent does in fact prevent the formation of the initial laminae of foam or whether such initial laminae are destroyed by the reagent before subsequent laminae of sufli-cient stability to produce a foam can be superimposed thereon. By foamingcomposition in the appended claims we mean a composition which is either actually foaming or which is capable of producing a foam under suitable conditions, e.g., by simply passing air through it.

In most instances, our reagents are effective to the extent that they destroy an existing foam substantially completely. In some instances, as when too little reagent is used and foam reduction may be slow or even incomplete, we intend that the description and our invention relate both to complete destruction and to pantial destruction of foams.

The proportions of our reagent required to be employed appear to vary widely. However, we generally use our reagent in amounts 1% by volume or less of the foaming composition. Usually, the amounts required will be between 0.1% and 0,0001%, by volume based on the volume of the foaming composition.

Our present reagents may be used in conjunction with any other effective and compatible anti-foamer. .It should also be stated that they are useful in conjunction with foam-inhibiting processes which are mechanical or electrical in character, rather than chemical. For example, some foams may be effectively destroyed by water sprays or jets. Incorporation of a small proportion of our reagents into such water sprays increase their effectiveness. U.S. Patent No. 2,240,495, to Dillon et 211., dated May 6, 1941, relates to a process for resolving foam by means of a high electrical potential. Incorporation of a small proportion of our present reagents into the foaming liquid increases the effectiveness of such electrical processes.

The following examples are presented to illustrate our invention.

A foam is efiected in a graduated cylinder containing mineral oil by bubbling nitrogen into the system. At equilibrium the height of the foam is measured and when the nitrogen is shut off, the time for the foam to drop is also measured. This procedure is repeated employing the compounds shown in the following table in ratios of 0.001% by volume in the oil. The presence of these compounds eifectively reduces the height of the foam that is formed and aids in its elimination.

ANTI-FOAMING AGENT Having thus described our invention, what we claim as new and desire to obtain by Letters Patent is:

1. A process for inhibiting :foam in a system susceptible to foaming which is characterized by subjecting said system to the action of a compound selected from the group consisting of Y (1) a branched polyalkylenepolyamine containing at least three primary amino groups and at least one tertiary amino group and having the formula wherein R is an alkylene group having at least two carbon atoms, x is an integer of 4 to 24, y is an integer of 1 to 6, and z is an integer of 0-6,

(2) an acylated branched polyalkylene polyamine containing at least three primary amino groups and at least one tertiary amino group and having the for- I NH: y

wherein R is an alkylene group having at least .two carbon atoms, x is an integer of 4 to 24, y is an integer of 1 to 6, and z is an integer of -6, formed by reacting, at a temperature of from about 120 C. to about 300 C., said .polyalkylenepolyamine with a compound selected from the group consisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction, (3) an oxylalkylated branched polyalkylenepolyamine containing at least three primary amino groups and at least one tertiary amino group and having the RNH:

i f :I

IYIH i NH: y

wherein 40 R is an alkylene group having at least two carbon l r NH:- R-N R1? RNH:

| i NH: y

wherein I R is an alkylene group having at least two carbon atoms,

x is an integer of 4 to 24,

y is an integer of 1 to 6, and

z is an integer of 0-6, formed by reacting, at a temperature of from about 7 100 C. to about 250 C., said polyalkylenepolyamine with a hydrocarbon halide alkylating agent having 1 to 30 carbon atoms,

(5 an olefinated branched polyalkylenepolyamine containing at least three primary amino groupsand at least one tertiary amino group and having the for- RNII;

1% t]. NHr Y wherein R is an alkylene group having at least two carbon atoms,

x is an integer of 4 to 24,

y is an integer of l to 6, and

z is an integer of 0-6, iformed by reacting, at a temperature of from about 70 C. to about C., said polyalkylenepolyamine with an olefinating agent selected from the group consisting of acrylonitrile, styrene, butadiene, vinyl ethers and vinyl sulfones,

(6) a Schiff base reaction product of a branched polyalkylenepolyamine containing at least three primary amino groups and at least one tertiary amino group and h-aving the formula wherein R is an alkylene group having at least two carbon atoms,

x is an integer of 4 to 24,

y is an integer of 1 to 6, and

z is an integer of 0-6, formed by reacting said polya'lkylenepolyamine with a compound selected from the group consisting of aldehydes and ketones,

(7) an acylated, then oxyalkylated branched polyalkyilenepolyam ine containing at least three primary amino groups and at least one tertiary amino group and having the hereinabove recited formula, formed 'by reacting, at a temperature of from about 125 C. to about 300 C., said polyalkyle-nepolyamine with an acylating agent selected Ifrom the group consisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction, and then reacting said acylated ipolyalkylenepolyamine, at a temperature of from about 80 C. to about 200 C. and a pressure of from about 10 p.s.i. to about 200 p.s.i., with an alkylene oxide having at least 2 carbon atoms,

(8) an oxyalkylated, then acylated branched polyalkylenepolyamine, containing at least three primary amino groups and at least one tertiary amino group and having the hereinabove recited formula, formed by reacting, at a temperature of from about 80 C. to about 200 C. and a pressure of from about 10 p.s.i. to about '200 p.s.i., said polyalkylenepolyamine with an alkylene oxide having at least 2 carbon atoms and then reacting said oxyalkylated polyaikylenepolyamine, at a temperature of firom about C. to about 300 C., with an acylating agent selected from the group consisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction,

(9) an alkylated, then acylated branched polyalkylenepolyamine containing at least three primary amino groups and at least one tertiary amino group and having the hereinabove recited formula, [formed by reacting, at a temperature of from about 100 C. to about 250 C., said polyalkylenepolyamine with a hydrocarbon halide alkylating agent having 1-30 carbon atoms, and then reacting said alkylated polyalkylenepolyamine, at a temperature of from about 120 C. to about 300 C., with an acylating agent selected [from the group consisting 'of (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction,

(10) an acylated, then alkylated branched polyalkylenepolyarnine containing at least three primary amino groups and at least one tertiary amino group and having the hereinabove recited formula, formed by reacting, at a temperature of from about 120 C. to about 300 C., said polyalkylenepolyamine with an acylating agent selected from the group consisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said 'carboxylic acid capable of forming said acid in said reaction, and then reacting said acylated polyalkylenepoly-amine, at a temperature of from about 100 C. to about 250 C, with a hydrocarbon halide alkylating agent having 1-30 carbon atoms,

(11) an oxyalkylated, then alkylated branched polyalkylenepolyamine containing at least three primary amino groups and at least one tertiary amino group and having the hereinabove recited formula, formed by reacting, at a temperature of from about 80 C. to about 200 C. and a pressure of from about 10 p.-s.i. to about 200 p.s.i., said polyalkylenepolyamine with an alkylene oxide having at least 2 carbon atoms, and then reacting said oxyalkylated polyallkylenepolyamine, at a temperature of from about 100 C. to about 250 C., with a hydrocarbon halide alkylating agent having '1-30 carbon atoms,

(12) a Schitf base reaction product of an acylated (13) a Schitf base reaction product of an alkylated branched polyalkylenepolyamine containing at least three primary amino groups and at least one tertiary amino group and having the hereinabout recited formula, formed by reacting, at a temperature of from about 100 C. to about 250 C., said polyalkylenetpolyamine with a hydrocarbon halide alkylating agent having 130 carbon atoms, and then reacting said alkylated polyalkylenepolyamine with a compound selected from the group consisting of aldehydes and ketones,

(14) an oxyalkylated Schiff base reaction product of a branched polyalkylenepolyamine containing at least three primary amino groups and at least one tertiary amino group and having the hereinabove recited formula, formed by reacting said polyalkylenepolyamine with a compound selected from the group consisting of aldehydes and ketones to form said SchiPf base reaction product and then reacting said Schiff base reaction product, at a temperature of from about 80 C. to about 200 C. and a pressure of from about 10 psi. to about 200 psi, with an alkylene oxide having at least 2 carbon atoms,

(15) an acylated, then o lefinated branched polyalkylenepolyarnine containing at 'least three primary amino groups and at least one tertiary amino group and having the hereinabove recited formula, formed by reacting, at a temperature of from about 120 C. to about 300 C., said polyalkylenepolyarnine with an acylating agent selected from the group consisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said react-ion, and then reacting said acylated polyalkylenepolyamine, at a temperature of from about 70 C. to about C., with an olefinating agent selected from the groups consisting of acrylonitrile, styrene, butadiene, vinyl ethers and vinyl sulfones, and

(16) an alkylated, then olefinated branched polya1kylenepolyamine containing at least three primary amino groups and at least one tertiary amino group and having the hereinabove recited formula, formed by reacting, at a temperature of from about 100 C. to about 250 C., said polyalkylenepolyamine with a hydrocarbon halide alkylating agent having from 130 carbon atoms, and then reacting said alkylated polyalkylenepolyamine, at a temperature of from about 70 C. to about 100 C., with an olefinating agent selected from the group consisting of acrylonitrile, styrene, butadiene, vinyl ethers and vinyl sulfiones.

2.. The process of claim 1 wherein the compound is a branched polyalkylenepolyamine containing at least three primary amino groups and at least one tertiary amino group and having the formula RIIIARNHQ R l IiIH Z l N z Y wherein wherein R is an alkylene group having at least two carbon atoms, x is an integer of 4 to 24, y is an integer of l to 6, and z is an integer of 0-6, formed by reacting at a temperature of from about C. to about 300 C., said polyalkylenepolyamine with a compound selected from the group consisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction. 4. The process of claim 1 wherein the compound is an oxyalkylated branched polyalkylenepolyamine containing RNH:

NH: y

wherein R is an alkylene group having at least two carbon atoms,

x is an integer of 4 to 24,

y is an integer of 1 to 6, and

z is an integer of -6, formed by reacting, at a temperature of from about 80 C. to about 200 C. and a pressure of from about p.s.i. to about 200 p.s.i., said polyalkylenepolyamine with an alkylene oxide having at least two carbon atoms.

5. The process of claim 1 wherein the compound is an alkylated branched polyalkylenepolyamine containing at least three primary amino groups and at least one tertiary amino group and having the formula wherein R is an alkylene group having at least two carbon atoms,

x is an integer of 4 to 24,

y is an integer of 1 to 6, and

z is an integer of 0-6, formed by reacting, at a temperature of from about 100 C. to about 250 C., said polyalkylenepolyamine with a hydrocarbon halide alkylating agent having 1 to 30 carbon atoms.

6. The process of claim 1 wherein the compound is an olefinated branched polyalkylenepolyamine containing at least three primary amino groups and at least one tertiary amino group and having the formula RN X r I NHa y RNH:

and at least one tertiary amino group and having the formula III NH2( R-N) (RN RNH:

wherein R is an alkylene group having at least two carbon atoms,

x is an integer of 4 to 24,

y is an integer of 1 to 6, and

z is an integer of 0-6, formed by reacting said polyalkylenepolyamine with a compound selected from the group consisting of aldehydes and ketones.

8. The process of claim 1 wherein the compound is an acylated, then oxyalkylated branched polyalkylenepolyamine containing at least three primary amino groups and at least one tertiary amino group and having the IE I NHz y RNI-Iz wherein R is an alkylene group having at least two carbon atoms,

x is an integer of 4 to 24,

y is an integer of 1 to 6, and

z is an integer of 0-6, formed by reacting, at a temperature of from about 125 C. to about 300 C., said polyalkylenepolyamine with an acylating agent selected from the group consisting of (i) a carboxylic acid having 7-39 carbon atoms and (ii) a precursor of said carboxylic acid capable of forming said acid in said reaction, and then reacting said acylated polyalkylenepolyarnine, at a temperature of from about C. to about 200 C. and a pressure of from about 10 p.s.i. to about 200 p.s.i., with an alkylene oxide having at least 2 carbon atoms.

References Cited by the Examiner UNITED STATES PATENTS 2,272,489 2/ 1942 Ulrich 260239 2,461,730 2/ 1949 Gunderson 252-321 2,493,453 1/1950 Gunderson 252321 2,528,273 10/1950 Gunderson 252321 2,583,771 1/1952 Gunderson 252321 2,588,343 3/1952 Bird et al. 252321 2,588,344 3/1952 Bird et al. 252321 2,600,361 6/1952 Gunderson 252321 2,647,088 7/1953 Gunderson 252321 3,056,687 10/1962 Stephan 252-358 3,060,210 10/1962 De Groote et al. 2528.55 3,133,941 5/1964 Edwards et al. 252392 FOREIGN PATENTS 233,766 5/1961 Australia.

ALBERT T. MEYERS, Primary Examiner.

JULIUS GREENWALD, Examiner.

H. B. GUYNN, Assistant Examiner. 

1. A PROCESS FOR INHIBITING FOAM IN A SYSTEM SUSCEPTIBLE TO FOAMING WHICH IS CHARACTERIZED BY SUBJECTING SAID SYSTEM TO THE ACTION OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF (1) A BRANCHED POLYALKYLENEPOLYAMINE CONTAINING LEAST THREE PRIMARY AMINO GROUPS AND AT LEAST ONE TERTIARY AMINO GROUP AND HAVING THE FORMULA NH2-(R-NH)X-(R-N(-(R-NH)Z-R-NH2))Y-R-NH2 WHEREIN R IS AN ALKYLENE GROUP HAVING AT LEAST TWO CARBON ATOMS, X IS AN INTEGER OF 4 TO 24 Y IS AN INTEGER OF 1 TO 6 Z IS AN INTEGER OF 0-6, (2) AN ACYLATED BRANCHED POLYALKYLENE POLYAMINE CONTAINING AT LEAST THREE PRIMARY AMINO GROUPS AND AT LEAST ONE TERTIARY AMINO GROUP AND HAVING THE FORMULA NH2-(R-NH)X-(R-N(-(R-NH)Z-R-NH2))Y-R-NH2 WHEREIN R IS AN ALKYLENE GROUP HAVING AT LEAST TWO CARBON ATOMS, X IS AN INTEGER OF 4 TO 24, Y IS AN INTEGER OF 1 TO 6, AND Z IS AN INTEGER OF 0.6, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 120*C. TO ABOUT 300*C., SAID POLYALKYLENEPOLYAMINE WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF (I) A CARBOXYLIC ACID HAVING 7-39 CARBON ATOMS AND (II) A PRECURSOR OF SAID CARBOXYLIC ACID CAPABLE OF FORMING SAID ACID IN SAID REACTION, (3) AN OXYLALKYLATED BRANCHED POLYALKYLENEPOLYAMINE CONTAINING AT LEAST THREE PRIMARY AMINO GROUPS AND AT LEAST ONE TERTIARY AMINO GROUP AND HAVING THE FORMULA NH2-(R-NH)X-(R-N(-(R-NH)Z-R-NH2))Y-R-NH2 WHEREIN R IS AN ALKYLENE GROUP HAVING AT LEAST TWO CARBON ATOMS, X IS AN INTEGER OF 4 TO 24, Y IS AN INTEGER OF 1 TO 6, AND Z IS AN INTEGER OF 0-6, FORMED BY REACTING AT A TEMPERATURE OF FROM ABOUT 80*C. TO ABOUT 200*C. AND A PRESSURE OF FROM ABOUT 10 P.S.I. TO ABOUT 200 P.S.I. SAID POLYALKYLENEPOLYAMINE WITH AN ALKYLENE OXIDE HAVING AT LEAST
 2. CARBON ATOMS, (4) ANN ALKYLATED BRANCHED POLYALKYLENEPOLYAMINE CONTAINING AT LEAST THREE PRIMARY AMINO GROUPS AND AT LEAST ONE TERTIARY AMINO GROUP AND HAVING THE FORMULA NH2-(R-NH)X-(R-N(-(R-NH)Z-R-NH2))Y-R-NH2 WHEREIN R IS AN ALKYLENE GROUP HAVING AT LEAST TWO CARBON ATOMS, X IS AN INTEGER OF 4 TO 24 Y IS AN INTEGER OF 1 TO 6, AND Z IS AN INTEGER OF 0-6, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 100*C. TO ABOUT 250*C., SAID POLYALKYLENEPOLYAMINE WITH A HYDROCARBON HALIDE ALKYLATING AGENT HAVING 1 TO 30 CARBON ATOMS, (5) AN OLEFINATED BRANCHED POLYALKYLENEPOLYAMINE CONTAINING AT LEAST THREE PRIMARY AMINO GROUPS AND AT LEAST ONE TERTIARY AMINO GROUP AND HAVING THE FORMULA NH2-(R-NH)X-(R-N(-(R-NH)Z-R-NH2))Y-R-NH2 WHEREIN R IS AN ALKYLENE GROUP HAVING AT LEAST TWO CARBON ATOMS, X IS AN INTEGER OF 4 TO 24 Y IS AN INTEGER OF 1 TO 6, AND Z IS AN INTEGER OF 0-6,& FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 70*C. TO ABOUT 100*C., SAID POLYALKYLENEPOLYAMINE WITH AN OLEFINATING AGENT SELECTED FROM THHE GROUP CONSISTING OF ACRYLONITRILE, STYRENE, BUTADIENE, VINYL ETHERS AND VINYL SULFONES, (6) A SCHIFF BASE REACTION PRODUCT OF A BRANCHED POLYALKYLENEPOLYAMINE CONTAINING AT LEAST THREE PRIMARY AMINO GROUPS AND AT LEAST ONE TERTIARY AMINO GROUP AND HAVING THE FORMULA NH2-(R-NH)X-(R-N(-(R-NH)Z-R-NH2))Y-R-NH2 WHEREIN R IS AN ALKYLENE GROUP HAVING AT LEAST TWO CARBON ATOMS, X IS AN INTEGER OF 4 TO 24, Y IS AN INTEGER OF 1 TO 6, AND Z IS AN INTEGER OF 0-6, FORMED BY REACTING SAID POLYALKYLENEPOLYAMINE WITH A COMPOUND SELECTED FROM THE GROUP CONSISTINGG OF ALDEHYDES AND KETONES, (7) AN ACYLATED, THEN OXYALKYLATED BRANCHED POLYALKYLENEPOLYAMINE CONTAING AT LAST THREE PRIMARY AMINO GROUPS AND AT LEAST ONE TERTIARY AMINO GROUP AND HAVING THE HEREIN ABOVE RECITED FORMULA, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 125* C. TO ABOUT 300*C., SAID POLYALKYLENEPOLYAMINE C. TO ABOUT 300*C., SAID POLYALKYLENEPOLYAMINE WITH AN ACYLATING AGENT SELECTED FROM THE GROUP CONSISTING OF (1) A CARBOXYLIC ACID HAVING 7-39 CARBON ATOMS AND (II) A PRECURSOR OF SAID CARBOXYLIC ACID CAPABLE OF FORMING SAID ACID IN SAID REACTION, AND THEN REACTING SAID ACYLATED POLYALKYLENEPOLYAMINE, AT A TEMPERATURE OF FROM ABOUT 80*C. TO ABOUT 200* C. AND A PRESSURE OF FROM ABOUT 10 P.S.I. TO ABOUT 200 P.S.I., WITH AN ALKYLENE OXIDE HAVING AT LEAST 2 CARBON ATOMS, (8) AN OXYALKYLATED, THEN ACYLATED BRANCHED POLYALKYLENEPOLYAMINE, CONTAINING AT LEAST THREE PRIMARY AMINO GROUPS AND AT LEAST ONE TERTIARY AMINO GROUP AND HAVING THE HEREINABOVE RECITED FORMULA, FORMED BY REACTING AT A TEMPERATURE OF FROM ABOUT 80* C. TO ABOUT 200*C. AND A PRESSURE OF FROM ABOUT 10 P.S.I. TO ABOUT 200 P.S.I., SAID POLYALKYLENEPOLYAMINE WITH AN ALKYLENE OXIDE HAVING AT LEAST 2 CARBON ATOMS AND THEN REACTING SAID OXYALKYLATED POLYALKYLENEPOLYAMINE, AT A TEMPERATURE OF FROM ABOUT 120*C. TO ABOUT 300*C., WITH AN ACYLATING AGENT SELECTED FROM THE GROUP CONSISTING OF (I) A CARBOXYLIC ACID HAVING 7-39 CARBON ATOMS AND (II) A PRECURSOR OF SAID CARBOXYLIC ACID CAPABLE OF FORMING SAID ACID IN SAID REACTION, (9) AN ALKYLATED, THEN ACYLATED BRANCHED POLYALKYLENE POLYAMINE CONTAINING AT LEAST THREE PRIMARY AMINO GROUPS AND AT LEAST ONE TERTIARY AMINO GROUP AND HAVING THE HEREINABOVE RECITED FORMULA, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 100*C. TO ABOUT 250*C., SAID POLYALKYLENEPOLYAMINE WITH A HYDROCARBON HALIDE ALKYLATING AGENT HAVING 1-30 CARBON ATOMS, AND THEN REACTING SAID ALKYLATED POLYALKYLENEPOLYAMINE, AT A TEMPERATURE OF FROM ABOUT 120*C. TO ABOUT 300*C., WITH AN ACYLATING AGENT SELECTED FROM THE GROUP CONSISTING OF (1) A CARBOXYLIC ACID HAVING 7-39 CARBON ATOMS AND (II) A PRECURSOR OF SAID CARBOXYLIC ACID CAPABLE OF FORMING SAID ACID IN SAID REACTION, (10) AN ACYLATED, THEN ALKYLATED BRONCHED POLYALKYLENEPOLYAMINE CONTAINING AT LEAST THREE PRIMARY AMINO GROUPS AND AT LEAST ONE TERTIARY AMINO GROUP AND HAVING THE HEREINABOVE RECITED FORMULA, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 120*C. TO ABOUT 300*C., SAID POLYALKYLENEPOLYAMINE WITH AN ACYLATING AGENT SELECTED FROM THE GROUP CONSISTING OF (I) A CARBOXYLIC ACID HAVING 7-39 CARBON ATOMS AND (II) A PRECURSOR OF SAID CARBOXYLIC ACID CAPABLE OF FORMING SAID ACID IN SAID REACTION, ANND THEN REACTING SAID ACYLATED POLYALKYLENEPOLYAMINE, AT A TEMPERATURE OF FROM ABOUT 100*C. TO ABOUT 250*C, WITH A HYDROCARBON HALIDE ALKYLATING AGENT HAVING 1-30 CARBON ATOMS, (11) AN OXYALKYLATED, THEN ALKYLATED BRANCHED POLYALKYLENEPOLYAMINE CONTAINING AT LEAST THREE PRIMARY AMINO GROUPS AND AT LEAST ONE TERTIARY AMINO GROUP AND HAVING THE HEREINABOVE RECITED FORMULA, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 80*C. TO ABOUT 200*C. AND A PRESSURE OF FROM ABOUT 10 P.S.I. TO ABOUT 2000 P.S.I., SAID POLYALKYLENEPOLYAMINE WITH AN ALKYLENE OXIDE HAVING AT LEAST 2 CARBON ATOMS, AND THEN REACTING SAID OXYLALKYLATED POLYALKYLENEPOLYAMINE, AT A TEMPERATURE OF FROM ABOUT 100*C. TO ABOUT 250*C., WITH A HYDROCARBON HALIDE ALKYLATING AGENT HAVING 1-30 CARBON ATOMS, (12) A SCHIFF BASE REACTION PRODUCT OF AN ACYLATED BRANCHED POLYALKYLENEPOLYAMINE CONTAINING AT LEAST THREE PRIMARY AMINO GROUPS AND AT LEAST ONE TERTIARY AMINO GROUP AND HAVING THE HEREINABOVE RECITED FORMULA, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 120*C. TO ABOUT 300*C., SAID POLYALKYLENEPOLYAMINE WITH AN ACYLATING AGENT SELECTED FROM THE GROUP CONSISTING OF (I) A CARBOXYLIC ACID HAVING 7-39 CARBON ATOMS AND (II) A PRECURSOR OF SAID CARBOXYLIC ACID CAPABLE OF FORMING SAID ACID IN SAID REACTION, AND THEN REACTING SAID ACYLATED POLYALKYLENEPOLYAMINE WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALDEHYDES AND KETONES, (13) A SCHIFF BASE REACTION PRODUCT OF AN ALKYLATED BRANCHED POLYALKYLENEPOLYAMINE CONTAINING AT LEAST THREE PRIMARY AMINO GROUPS AND AT LEAST ONE TERTIARY AMINO GROUP AND HAVING THE HEREINABOUT RECITED FORMULA, FORMED BY REACTING, AT A TEMPERATURE OF FROM ABOUT 100*C. TO ABOUT 250*C., SAID POLYALKYLENEPOLYAMINE WITH A HYDROCARBON HALIDE ALKYLATING AGENT HAVING 1-30 CARBON ATOMS, AND THEN REACTING SAID ALKYLATED POLYALKYLENEPOLYAMINE WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF ALDEHYDES AND KETONES, (14) AN OXYALKYLATED SCHIFF BASE REACTION PRODUCT OF A BRANCHHED 